WO2011065382A1 - Processing aid for polyolefin resins, polyolefin resin compositions, and molded products - Google Patents
Processing aid for polyolefin resins, polyolefin resin compositions, and molded products Download PDFInfo
- Publication number
- WO2011065382A1 WO2011065382A1 PCT/JP2010/070936 JP2010070936W WO2011065382A1 WO 2011065382 A1 WO2011065382 A1 WO 2011065382A1 JP 2010070936 W JP2010070936 W JP 2010070936W WO 2011065382 A1 WO2011065382 A1 WO 2011065382A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyolefin resin
- processing aid
- alkyl methacrylate
- examples
- mass
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/12—Esters of monohydric alcohols or phenols
- C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Definitions
- the present invention relates to a processing aid for polyolefin resin, a polyolefin resin composition containing the processing aid for polyolefin resin, and a molded product obtained by molding the polyolefin resin composition.
- Polyolefin-based resins are widely used in various applications because they are lightweight, have excellent physical properties such as rigidity, heat resistance, and chemical resistance, and are excellent in recyclability. In particular, since it has excellent mechanical and chemical properties, it is widely used in the fields of automobile members, household appliance members, medical members, building members, packaging materials, and the like.
- the moldability is never satisfactory, and various methods have been proposed to improve the moldability. For example, in order to improve the molding processability of polyolefin resin, a method of increasing the melt tension by increasing the molecular weight of polyolefin resin has been proposed. As a result, there is a problem that both excellent melt tension and excellent fluidity cannot be achieved.
- Patent Document 1 proposes a method in which an alkyl methacrylate polymer having a mass average molecular weight of 150,000 to 20 million is blended with a polyolefin resin.
- Patent Document 2 proposes a method of adding an alkyl (meth) acrylate polymer having a long-chain alkyl group to a polyolefin resin.
- An object of the present invention is to provide a processing aid for polyolefin resin that provides a polyolefin resin composition that is excellent in molding processability, that is, excellent in melt tension, fluidity, and eye stain suppression effect.
- the present invention includes an alkyl methacrylate polymer (A) containing an alkyl methacrylate (a1) unit having an alkyl group having 2 to 10 carbon atoms as a main component and having a mass average molecular weight of 15,000 to 145,000.
- a processing aid for polyolefin resins is provided.
- the present invention also provides a polyolefin resin composition comprising the polyolefin resin processing aid and the polyolefin resin (B). Furthermore, this invention provides the molded article obtained by shape
- the processing aid for polyolefin resin of the present invention is excellent in powder handling property and blended with the polyolefin resin (B), so that it has excellent molding processability, that is, melt tension, fluidity, and eye strain suppression effect.
- An excellent polyolefin resin composition is provided.
- Sectional views of atypical dies used in Examples 22 and 23 and Comparative Examples 24 to 27 are shown.
- the relationship between the mass average molecular weight and MFR in Examples 8 to 10 and Comparative Examples 10 to 12 is shown.
- the relationship between the mass average molecular weight and the melt tension in Examples 8 to 10 and Comparative Examples 10 to 12 is shown.
- the alkyl methacrylate polymer (A) of the present invention is mainly composed of alkyl methacrylate (a1) units having 2 to 10 carbon atoms in the alkyl group.
- the content of alkyl methacrylate (a1) units having 2 to 10 carbon atoms in the alkyl group is 50% by mass or more in 100% by mass of all monomer units, and (a1)
- the unit content is preferably 70% by mass or more, and the (a1) unit content is more preferably 80% by mass or more.
- the content of the alkyl methacrylate (a1) unit having 2 to 10 carbon atoms in the alkyl group is 50% by mass or more, the polyolefin resin processing in the polyolefin resin (B) of the resulting polyolefin resin composition
- the dispersibility of the auxiliary agent becomes good and the melt tension is excellent.
- the alkyl methacrylate polymer (A) of the present invention can be obtained by polymerizing the monomer component (a) whose main component is an alkyl methacrylate (a1) having 2 to 10 carbon atoms in the alkyl group.
- alkyl methacrylate (a1) having 2 to 10 carbon atoms in the alkyl group include, for example, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, sec-butyl methacrylate, t- Examples thereof include butyl methacrylate, 2-methylbutyl methacrylate, 3-methylbutyl methacrylate, 3-pentyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, dec
- the processing aid for the polyolefin resin obtained is excellent in powder handling properties, alkyl methacrylates having an alkyl group with 2 to 6 carbon atoms are preferred, and the polyolefin resin of the resulting polyolefin resin composition ( Since the dispersibility of the processing aid for polyolefin resin in B) is good and the melt tension is excellent, alkyl methacrylate having 4 carbon atoms in the alkyl group is more preferred, and the melt tension of the resulting polyolefin resin composition is I-Butyl methacrylate is more preferred because of its excellent fluidity improving effect.
- the monomer component (a) in addition to the alkyl methacrylate (a1) having 2 to 10 carbon atoms in the alkyl group, other monomer (a2) that can be copolymerized may be included as necessary.
- the other monomer (a2) include methyl methacrylate; alkyl methacrylate having 10 or more carbon atoms in the alkyl group such as lauryl methacrylate; (meth) acrylic acid; aromatic such as styrene, ⁇ -methylstyrene, chlorostyrene, etc.
- Group vinyl monomers alkyl acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate; vinyl cyanide monomers such as (meth) acrylonitrile; vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether; vinyl acetate and butyric acid Carboxylic acid vinyl monomers such as vinyl; Olefin monomers such as ethylene, propylene and isobutylene; Diene monomers such as butadiene, isoprene and dimethylbutadiene; 4- (meth) acryloyloxy-2,2,6 , 6-Tetramethylpiperidi 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine light stabilizing capability group-containing monomers, and the like. These may be used alone or in combination of two or more.
- alkyl acrylate is preferable because it has good copolymerizability with alkyl methacrylate having 2 to 10 carbon atoms in the alkyl group and suppresses thermal decomposition of the alkyl methacrylate polymer (A).
- (meth) acryl means “acryl” or “methacryl”.
- the composition ratio of the monomer component (a) is such that the content of the alkyl methacrylate (a1) having 2 to 10 carbon atoms in the alkyl group is 50% by mass or more in 100% by mass of the monomer component (a).
- the content of the monomer (a2) is preferably 50% by mass or less, the content of (a1) is preferably 70% by mass or more, and the content of (a2) is preferably 30% by mass or less, (a1) It is more preferable that the content of is 80% by mass or more and the content of (a2) is 20% by mass or less.
- the processing aid for polyolefin resin in the polyolefin resin (B) of the resulting polyolefin resin composition is used.
- the dispersibility of the agent is improved and the melt tension is excellent.
- the content of the other monomer (a2) is 50% by mass or less, the dispersibility of the processing aid for polyolefin resin in the polyolefin resin (B) of the resulting polyolefin resin composition becomes good. Excellent melt tension.
- Examples of the polymerization method of the monomer component (a) include radical polymerization and ionic polymerization. Among these, radical polymerization is preferable because of good productivity.
- Examples of the polymerization form of the monomer component (a) include emulsion polymerization, soap-free polymerization, fine suspension polymerization, suspension polymerization, bulk polymerization, and solution polymerization. Among these, emulsion polymerization and suspension polymerization are preferable because the alkyl methacrylate polymer (A) is obtained in a powdery or granular form.
- Examples of the emulsifier used when the monomer component (a) is polymerized by emulsion polymerization include an anionic emulsifier, a nonionic emulsifier, a polymer emulsifier, and a reactivity having an unsaturated double bond capable of radical polymerization in the molecule.
- Emulsifiers may be used alone or in combination of two or more.
- anionic emulsifiers such as sulfonic acid salt compounds, sulfuric acid salt compounds, and phosphate ester salt compounds are preferable.
- Examples of the dispersion stabilizer used when the monomer component (a) is polymerized by suspension polymerization include poorly water-soluble inorganic compounds such as calcium phosphate, calcium carbonate, aluminum hydroxide, and starch silica; polyvinyl alcohol, polyethylene oxide, Nonionic polymer compounds such as cellulose derivatives; anionic polymer compounds such as poly (meth) acrylic acid and salts thereof, and copolymers of methacrylic acid esters and methacrylic acid and salts thereof. These may be used alone or in combination of two or more. Among these, an anionic polymer compound is preferable because the dispersion stability can be maintained with a very small amount.
- Examples of the polymerization initiator used for the polymerization of the monomer component (a) include persulfate compounds such as potassium persulfate, sodium persulfate and ammonium persulfate; azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2-phenylazo-4 Oil-soluble azo compounds such as methoxy-2,4-dimethylvaleronitrile; 2,2′-azobis ⁇ 2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide ⁇ 2,2′-azobis ⁇ 2-methyl-N- [2- (1-hydroxyethyl)] propionamide ⁇ , 2,2′-azobis ⁇ 2-methyl-N- [2- (1 Hydroxybutyl)] propionamide ⁇ , 2,2′-azobis [2-(5)
- the alkyl methacrylate polymer (A) polymerized by various polymerization methods may be taken out of the polymerization system as powder or granules by a method suitable for each polymerization method.
- examples of the method for taking out the polymer (A) from the latex of the polymer (A) include a coagulation method, a spray drying method, a centrifugal separation method, A freeze-drying method is mentioned.
- the coagulation method and the spray drying method are preferred because the uniformity of the resulting powder of the alkyl methacrylate polymer (A) becomes good.
- the alkyl methacrylate polymer (A) latex is brought into contact with a coagulant, and coagulated while stirring to form a slurry, followed by dehydration drying, whereby the alkyl methacrylate polymer (A) powder is obtained.
- the method of obtaining a body is mentioned.
- the coagulant include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; organic acids such as formic acid and acetic acid; inorganic salts such as aluminum sulfate, magnesium sulfate, and calcium sulfate; and organic salts such as calcium acetate. .
- the alkyl methacrylate polymer (A) latex is spray-dried with a spray dryer under the conditions of an inlet temperature of 120 ° C. to 220 ° C. and an outlet temperature of 40 to 90 ° C.
- a method for obtaining a powder of the combined body (A) is mentioned.
- the outlet temperature in the spray drying method is preferably 40 to 90 ° C., and preferably 40 to 80 ° C., because the powder of the alkyl methacrylate polymer (A) has excellent crushability to primary particles. It is more preferable.
- the mass average molecular weight of the alkyl methacrylate polymer (A) of the present invention is from 15,000 to 145,000, preferably from 20,000 to 130,000, and more preferably from 25,000 to 100,000. .
- the mass average molecular weight of the alkyl methacrylate polymer (A) is 15,000 or more, the effect of improving the melt tension of the resulting polyolefin resin processing aid is excellent.
- liquidity of the polyolefin resin composition obtained as the mass average molecular weight of an alkyl methacrylate polymer (A) is 145,000 or less.
- the mass average molecular weight in this invention is measured using a gel permeation chromatography.
- Examples of the method for adjusting the mass average molecular weight include a method for adjusting the amount of the polymerization initiator and a method for adjusting the amount of the chain transfer agent.
- Examples of chain transfer agents include mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, n-tetradecyl mercaptan, n-hexyl mercaptan; halides such as carbon tetrachloride and ethylene bromide; ⁇ -methylstyrene dimer may be mentioned. These may be used alone or in combination of two or more.
- the amount of chain transfer agent used can be appropriately adjusted according to the weight average molecular weight of the alkyl methacrylate polymer (A), the type of chain transfer agent used, the composition ratio of the monomer component (a), and the like. .
- alkyl methacrylate polymer (A) of the present invention the same polymer may be used alone, or two or more polymers having different compositions, molecular weights, particle sizes, etc. may be used in combination.
- the processing aid for polyolefin resin of the present invention contains the alkyl methacrylate polymer (A) of the present invention.
- the processing aids for polyolefin resins are fillers, flame retardants, stabilizers, lubricants, foaming agents as long as they do not impair the original properties of polyolefin resins (B) in addition to alkyl methacrylate polymers (A).
- Various additives such as these may be further blended.
- the same additives as those exemplified for the additive to be added to the polyolefin resin composition described later can be used.
- the polyolefin resin (B) used in the present invention is a homopolymer or copolymer of an olefin monomer, a copolymer of a dominant amount of an olefin monomer and a subordinate amount of a vinyl monomer, an olefin type
- the main component is a copolymer of a monomer and a diene monomer.
- the olefin monomer include ethylene, propylene, 1-butene, 1-hexene, 1-octene and 1-decene.
- ethylene and propylene are preferable from the viewpoint of versatility of the obtained molded body.
- polystyrene resin (B) examples include low density polyethylene, ultra low density polyethylene, ultra low density polyethylene, linear low density polyethylene, high density polyethylene, ultra high molecular weight polyethylene, polypropylene, ethylene-propylene copolymer, polybutene. And ethylene-vinyl acetate copolymer. These may be used alone or in combination of two or more. Among these, polyethylene, polypropylene, an ethylene-propylene copolymer, and an ethylene-vinyl acetate copolymer are preferable from the viewpoint of versatility of the obtained molded body.
- polyethylene examples include “Novatech HD HJ360”, “Novatech HD HY420”, “Novatech HD HE421”, “Novatech HD JF313” (trade name, manufactured by Nippon Polyethylene Co., Ltd.); “Hi-X” (trade name, Co., Ltd.) ) Prime polymer); “Mineron”, “Mineace”, “Minefan” (trade name, Sankyo Polyethylene Co., Ltd.).
- polypropylene examples include “Novatech PP FY4”, “Novatech PP MA3”, “Novatech PP BC03B”, “Novatech PP BC06C”, “Wintech”, “Newcon”, “Newformer” (trade name, Japan) Polypro Co., Ltd.); “Prime Polypro J105G”, “Prime Polypro B241” (trade name, manufactured by Prime Polymer Co., Ltd.).
- thermoplastic elastomer (C) used in the present invention examples include thermoplastic elastomers such as olefin elastomers, styrene elastomers, polyester elastomers, polyamide elastomers, polyurethane elastomers; natural rubber, polyisobutylene, polyisoprene, chloroprene. Natural or synthetic rubbers such as rubber, butyl rubber, nitrile butyl rubber and the like can be mentioned. These may be used alone or in combination of two or more. Among these, an olefin elastomer and a styrene elastomer are preferable from the viewpoint of versatility of the obtained molded body.
- olefin elastomer examples include non-ethylene copolymers such as ethylene-propylene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM), ethylene-1-butene copolymer, and ethylene-1-octene copolymer.
- EPR ethylene-propylene copolymer
- EPDM ethylene-propylene-diene copolymer
- ethylene-1-butene copolymer ethylene-1-butene copolymer
- ethylene-1-octene copolymer examples include crystalline or microcrystalline ethylene- ⁇ -olefin copolymers; polybutenes; chlorinated polyethylenes; partially crosslinked products or completely crosslinked products obtained by crosslinking polyethylene, polypropylene, and EPDM. These may be used alone or in combination of two or more.
- styrene elastomers include block copolymers such as styrene-butadiene-styrene copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), and styrene-isoprene / butadiene-styrene copolymer (SIBS).
- SBS styrene-butadiene-styrene copolymer
- SIS styrene-isoprene-styrene copolymer
- SIBS styrene-isoprene / butadiene-styrene copolymer
- Styrene-ethylene-butene-styrene copolymer SEBS
- hydrogenated SEBS SEBS
- styrene-ethylene-propylene-styrene copolymer SEPS
- styrene-butadiene-butylene-styrene copolymer partially hydrogenated styrene
- a part of a block copolymer such as a butadiene-styrene copolymer or a completely hydrogenated product. These may be used alone or in combination of two or more.
- the polyolefin resin composition of the present invention contains a polyolefin resin processing aid and a polyolefin resin (B), and further contains a thermoplastic elastomer (C) as necessary.
- the contents of the polyolefin resin (B) and the thermoplastic elastomer (C) can be appropriately set according to the use of the obtained molded product.
- a resin in which the polyolefin resin (B) and the thermoplastic elastomer (C) are already blended may be used.
- resins include “Miralastomer 5030N”, “Miralastomer 6030N”, “Miralastomer 7030N”, “Miralastomer 8030N”, “Miralastomer 2600B” (trade name, manufactured by Mitsui Chemicals, Inc.); “Thermo Run 5850N”, “Thermo Run 3855B” (trade name, manufactured by Mitsubishi Chemical Corporation); “Esporex 3785", “Esporex 820", “Esporex 822” (trade name, manufactured by Sumitomo Chemical Co., Ltd.); “Santplane 101-55”, “Santplane 121-68W228”, “Santplane 121-50M100” (trade name, manufactured by ExxonMobil Co., Ltd.). These may be used alone
- the blending amount of the processing aid for polyolefin resin of the present invention is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass in total of the polyolefin resin (B) and the thermoplastic elastomer (C). More preferably, it is 0.5 to 10 parts by mass.
- the blending amount of the processing aid for polyolefin resin is 0.1 parts by mass or more, the melt tension and fluidity of the resulting polyolefin resin composition are excellent.
- the original characteristic of polyolefin resin (B) is not impaired as the said compounding quantity of the processing aid for polyolefin resin is 20 mass parts or less.
- the total of 100 parts by mass of the polyolefin resin (B) and the thermoplastic elastomer (C) includes the case where the thermoplastic elastomer (C) is 0 part by mass.
- the polyolefin resin composition may further contain various additives such as a filler, a flame retardant, a stabilizer, a lubricant, a foaming agent, a plasticizer, and a rubber softener as necessary.
- a filler examples include calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, magnesium hydroxide, aluminum hydroxide, talc, mica, kaolin, titanium white, white carbon, carbon black, glass fiber, and carbon fiber. . These may be used alone or in combination of two or more.
- the blending amount of the filler is preferably 0.1 to 400 parts by mass with respect to 100 parts by mass in total of the polyolefin resin (B) and the thermoplastic elastomer (C).
- the blending amount of the filler is 0.1 parts by mass or more, the blending effect of the filler is sufficiently exhibited. Moreover, the original characteristic of polyolefin resin (B) is not impaired as the said compounding quantity of a filler is 400 mass parts or less.
- the flame retardant examples include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, diisopropylphenyl phosphate, tris (chloroethyl) ) Phosphate ester compounds such as phosphate, alkoxy-substituted bisphenol A bisphosphate, hydroquinone bisphosphate, resorcin bisphosphate, trioxybenzene triphosphate; tetrabromobisphenol A, decabromodiphenyl oxide, hexabromocyclododecane, octabromodiphenyl ether, bistribromo Phenoxyethane, ethylene Strebrobromophthalimide, tribrom
- the blending amount of the flame retardant is preferably 10 to 200 parts by mass with respect to a total of 100 parts by mass of the polyolefin resin (B) and the thermoplastic elastomer (C), although it depends on the type of flame retardant.
- the stabilizer examples include pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-t-butyl- 5-methyl-4-hydroxyphenyl) propionate] and the like; phosphorus antioxidants such as tris (monononylphenyl) phosphite and tris (2,4-di-t-butylphenyl) phosphite Sulfur-based antioxidants such as dilauryl thiodipropionate; “Tinuvin-770” (trade name, manufactured by Ciba Japan Co., Ltd.), “Adekastab LA-57” (trade name, manufactured by ADEKA Corporation) Hindered amine light stabilizers such as “Tinuvin 1577FF” (trade name, manufactured by Ciba Japan Co., Ltd.), “Adeka Stub LA-32” (Trade name, (Ltd.)
- lubricant examples include sodium, calcium or magnesium salts of lauric acid, palmitic acid, oleic acid or stearic acid.
- Examples of the foaming agent include inorganic foaming agents, volatile foaming agents, and decomposable foaming agents.
- examples of the inorganic foaming agent include carbon dioxide, air, and nitrogen.
- Examples of the volatile blowing agent include aliphatic hydrocarbons such as propane, n-butane, i-butane and pentane; cycloaliphatic hydrocarbons such as cyclobutane and cyclopentane; trichlorofluoromethane, dichlorodifluoromethane and dichloromethane.
- Halogenated hydrocarbons such as tetrafluoroethane, methyl chloride, ethyl chloride, methylene chloride and the like can be mentioned.
- Examples of the decomposable foaming agent include azodicarbonamide, dinitrosopentamethylenetetramine, azobisisobutyronitrile, and sodium bicarbonate. These foaming agents may be used individually by 1 type, and may use 2 or more types together.
- the blending amount of the foaming agent is 0.1 to 25 parts by mass with respect to a total of 100 parts by mass of the polyolefin resin (B) and the thermoplastic elastomer (C), although it depends on the type of the foaming agent. preferable.
- the rubber softener is generally a mixture of an aromatic ring, a naphthene ring, and a paraffin chain.
- process oils called paraffin and process oils called naphthenic are used among mineral oil rubber softeners.
- white oil, mineral oil Ethylene and ⁇ -olefin oligomers, low molecular weight polybutadiene, low molecular weight polybutadiene, paraffin wax, and liquid paraffin can be used.
- paraffinic process oil is preferably used.
- rubber softeners examples include NA Solvent (isoparaffinic hydrocarbon oil, trade name) manufactured by NOF Corporation, PW-90 (n-paraffinic process oil, trade name) of Idemitsu Kosan Co., Ltd., IP-solvent 2835 (synthetic isoparaffinic hydrocarbon, 99.8% by mass or more isoparaffin, trade name) manufactured by Idemitsu Petrochemical Co., Ltd., neothiozole (n-paraffinic process oil, product manufactured by Sanko Chemical Co., Ltd.) Name). These may be used alone or in combination of two or more.
- the blending amount of the rubber softening agent is preferably 10 to 300 parts by mass, more preferably 50 to 200 parts by mass with respect to 100 parts by mass in total of the polyolefin resin (B) and the thermoplastic elastomer (C). Part.
- the blending amount of the rubber softener is 10 parts by mass or more, the flexibility imparting effect is sufficiently exhibited.
- the original characteristic of polyolefin resin (B) is not impaired as the said compounding quantity of the softener for rubbers is 300 mass parts or less.
- additives such as fillers, flame retardants, stabilizers, lubricants, foaming agents, plasticizers, rubber softeners, etc. are not sufficiently blended when not sufficiently dispersed in the polyolefin resin (B). It may become.
- the processing aid for polyolefin resin of the present invention not only the molding processability of the resulting polyolefin resin composition is improved, but also the dispersibility of various additives in the polyolefin resin (B) is improved. In order to improve, further blending effects can be expected. Moreover, the effect which suppresses the bleed-out of various additives with low compatibility with polyolefin resin (B) can be anticipated by mix
- the polyolefin resin composition of the present invention comprises a polyolefin resin processing aid, a polyolefin resin (B), and if necessary, a thermoplastic elastomer (C) and various additives, followed by extrusion kneading and roll kneading. It adjusts by melt-kneading by well-known methods, such as.
- the polyolefin resin processing aid of the present invention, the polyolefin resin (B), and if necessary, the thermoplastic elastomer (C) and various additives may be melt kneaded in a lump.
- thermoplastic elastomer (C) After preparing a master batch by mixing a part of the processing aid for thermoplastic resin and the thermoplastic elastomer (C), the remainder of the polyolefin resin (B), if necessary, part of the thermoplastic elastomer (C)
- the various additives may be mixed in multiple stages.
- the molded article of the present invention can be obtained by molding the polyolefin resin composition of the present invention.
- the molding method include extrusion molding, injection molding, calendar molding, blow molding, thermoforming, foam molding, and melt spinning.
- the molded article of the present invention is suitable for automobile members, home appliance members, medical members, building members, and packaging materials because the resulting polyolefin resin composition is excellent in melt tension and fluidity.
- Mass average molecular weight and molecular weight distribution The mass average molecular weight and number average molecular weight of the resulting alkyl methacrylate polymer (A) are gel permeation using the tetrahydrofuran solubles of the alkyl methacrylate polymer (A) as a sample.
- the melt tension is one of the indicators for determining the moldability such as extrusion moldability, blow moldability, and foam moldability, and the improvement of the melt tension can be regarded as the improvement of the moldability.
- Example 1 In a separable flask (capacity 5 liters) equipped with a thermometer, nitrogen introduction tube, cooling tube and stirrer, 300 parts (3,000 grams) of deionized water, 98 parts of i-butyl methacrylate, 2 parts of n-butyl acrylate Then, 0.22 parts of n-octyl mercaptan and 1.1 parts of sodium dodecylbenzenesulfonate were added, and the atmosphere in the flask was replaced with nitrogen by passing a nitrogen stream through the separable flask. Next, the internal temperature was raised to 60 ° C., and 0.15 part of potassium persulfate and 5 parts of deionized water were added.
- alkyl methacrylate polymer (A1) latex was obtained.
- the resulting latex of alkyl methacrylate polymer (A1) was dropped into 400 parts of 70 ° C. hot water containing 5 parts of calcium acetate, and then heated to 90 ° C. for coagulation.
- the obtained coagulated product was separated and washed, and then dried at 60 ° C. for 16 hours to obtain an alkyl methacrylate polymer (A1).
- the mass average molecular weight of the polymer (A1) was 110,000, and the molecular weight distribution was 1.9.
- the obtained alkyl methacrylate polymer (A1) was used as a polyolefin resin processing aid (1).
- Table 1 The results of evaluating the powder handling property of the processing aid (1) are shown in Table 1.
- Alkyl methacrylate polymers (A2) to (A13) were obtained in the same manner as in Example 1 except that the composition of the monomer components and the amount of chain transfer agent were changed as shown in Table 1.
- the resulting alkyl methacrylate polymers (A2) to (A13) were used as polyolefin resin processing aids (2) to (13).
- This emulsified mixture was charged into a separable flask equipped with a thermometer, a nitrogen introduction tube, a cooling tube and a stirrer, and the internal temperature was raised to 60 ° C. under a nitrogen atmosphere.
- 0.0001 part of ferrous sulfate, ethylenediamine 0.0003 part of acetic acid disodium salt, 0.3 part of Rongalite and 5 parts of deionized water were added. Thereafter, heating and stirring were continued for 2 hours to complete the polymerization, and an alkyl methacrylate polymer (A14) latex was obtained.
- the resulting latex of alkyl methacrylate polymer (A14) was dripped into 400 parts of 25 ° C.
- alkyl methacrylate polymer (A14) was used as a polyolefin resin processing aid (14).
- alkyl methacrylate polymer (A16) latex was obtained.
- the resulting latex of the alkyl methacrylate polymer (A16) was dropped into 400 parts of 70 ° C. hot water containing 5 parts of calcium acetate, and then heated to 90 ° C. for coagulation.
- the obtained coagulated product was separated and washed, and then dried at 60 ° C. for 16 hours to obtain an alkyl methacrylate polymer (A16).
- the obtained alkyl methacrylate polymer (A16) was used as a polyolefin resin processing aid (16).
- i-BMA i-butyl methacrylate MMA: methyl methacrylate EMA: ethyl methacrylate n-BMA: n-butyl methacrylate LMA: lauryl methacrylate n-BA: n-butyl acrylate i-BA: i-butyl acrylate tBH: t-butyl hydro Peroxide nOM: n-octyl mercaptan
- the mixture was melt-kneaded under the conditions of a screw rotation speed of 30 rpm and a barrel temperature of 190 ° C. to obtain a profile extrusion molded product.
- the molded product extruded from the odd-shaped die was taken at a constant speed parallel to the extrusion direction, and cut when it was taken 20 cm.
- Table 4 shows the moldability of the obtained profile extrusion-molded product and the evaluation results of the eyes.
- the processing aids (1) to (7) for polyolefin resins of Examples 1 to 7 have good handling properties as powders.
- the processing aids (1) to (7) are easily mixed with the polyolefin resin when hand blended and can be stably supplied with a feeder or the like, so that they can be uniformly kneaded with the polyolefin resin.
- the polyolefin resin processing aid (8) having a mass average molecular weight lower than the range of the present invention was agglomerated and poor in handling as a powder (Comparative Example 1).
- the polyolefin resin processing aids (14) and (15) whose monomer units are out of the scope of the present invention are high-viscosity paste-like materials, and thus the handling properties as powders were poor ( Comparative Examples 7 and 8). Supply with a hand blend or a feeder is difficult, and use as a processing aid is difficult.
- the polyolefin resin compositions containing the processing aids (1) to (7) for polyolefin resins of the present invention were excellent in melt tension and MFR (Examples 8 to 21). ).
- a polyolefin resin composition not containing a polyolefin processing aid did not have a sufficient balance between melt tension and MFR and was inferior in molding processability (Comparative Examples 17 and 23).
- the polyolefin resin composition containing the polyolefin resin processing aid (8) having a mass average molecular weight below the range of the present invention did not improve the melt tension (Comparative Examples 10 and 18).
- Polyolefin resin compositions containing polyolefin resin processing aids (9) to (12) having a mass average molecular weight exceeding the range of the present invention have an inadequate balance between melt tension and MFR and are inferior in molding processability.
- the processing aid for polyolefin resin (13) in which the carbon number of the alkyl group of the alkyl methacrylate unit is outside the range of the present invention has insufficient dispersibility in the polyolefin resin (Comparative Examples 15 and 22). .
- Comparative Example 15 since the compatibility with the polyolefin resin (B) was low and the strand could not be taken up, the melt tension could not be measured. In Comparative Example 22, the melt tension was low.
- the type of monomer unit is outside the scope of the present invention, and the polyolefin resin composition containing the processing aid for polyolefin resin (16) polymerized in two stages does not have a sufficient balance between melt tension and MFR.
- the molding processability was inferior (Comparative Example 16).
- the polyolefin resin composition to which the processing aid for polyolefin resin according to the present invention was added was excellent in the effect of suppressing eye strain as well as improved moldability (Examples 22 and 23).
- the polyolefin resin composition containing the processing aids for polyolefin resins (9) and (10) having a mass average molecular weight exceeding the range of the present invention, and the types of monomer units are outside the scope of the present invention.
- the polyolefin resin composition containing the processing aid (16) for polyolefin resin polymerized in stages was inferior in molding processability and the effect of suppressing eye strain (Comparative Examples 24-26).
- FIG. 2 shows the relationship between the weight average molecular weights of Examples 8 to 10 and Comparative Examples 10 to 12 and MFR.
- the processing aids for polyolefin resins of Examples 8 to 10 and Comparative Examples 10 to 12 are composed of the same monomer component and have different mass average molecular weights.
- FIG. 2 it can be seen that there is a correlation between the mass average molecular weight of the polyolefin resin processing aid and the fluidity of the polyolefin resin composition containing the polyolefin processing aid.
- FIG. 3 showing the relationship between the mass average molecular weight and the melt tension, it can be seen that the melt tension is particularly excellent in the range of the mass average molecular weight of the present invention.
- the polyolefin resin composition containing the processing aid for polyolefin resin according to the present invention is excellent in molding processability, that is, excellent in melt tension, fluidity, and eye stain suppression effect. It is suitable for a member for home use, a member for home appliance, a member for medical use, a member for construction, and a packaging material.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
しかしながら、その成形加工性は決して満足できるものではなく、成形加工性を改良するため、様々な方法が提案されている。例えば、ポリオレフィン系樹脂の成形加工性を改良するために、ポリオレフィン系樹脂を高分子量化して溶融張力を高くする方法が提案されているが、高分子量化により成形加工性の一つの指標である流動性が低下するため、優れた溶融張力と優れた流動性が両立できないという課題があった。 Polyolefin-based resins are widely used in various applications because they are lightweight, have excellent physical properties such as rigidity, heat resistance, and chemical resistance, and are excellent in recyclability. In particular, since it has excellent mechanical and chemical properties, it is widely used in the fields of automobile members, household appliance members, medical members, building members, packaging materials, and the like.
However, the moldability is never satisfactory, and various methods have been proposed to improve the moldability. For example, in order to improve the molding processability of polyolefin resin, a method of increasing the melt tension by increasing the molecular weight of polyolefin resin has been proposed. As a result, there is a problem that both excellent melt tension and excellent fluidity cannot be achieved.
また、特許文献2では、ポリオレフィン系樹脂に長鎖アルキル基を有するアルキル(メタ)アクリレート重合体を添加する方法が提案されている。 As a method for solving these problems,
また、本発明は、該ポリオレフィン系樹脂用加工助剤及びポリオレフィン系樹脂(B)を含むポリオレフィン系樹脂組成物を提供する。
更に、本発明は、該ポリオレフィン系樹脂組成物を成形して得られる成形品を提供する。 The present invention includes an alkyl methacrylate polymer (A) containing an alkyl methacrylate (a1) unit having an alkyl group having 2 to 10 carbon atoms as a main component and having a mass average molecular weight of 15,000 to 145,000. A processing aid for polyolefin resins is provided.
The present invention also provides a polyolefin resin composition comprising the polyolefin resin processing aid and the polyolefin resin (B).
Furthermore, this invention provides the molded article obtained by shape | molding this polyolefin resin composition.
アルキルメタクリレート系重合体(A)は、全単量体単位100質量%中、アルキル基の炭素数が2~10のアルキルメタクリレート(a1)単位の含有率が50質量%以上であり、(a1)単位の含有率が70質量%以上であることが好ましく、(a1)単位の含有率が80質量%以上であることがより好ましい。
アルキル基の炭素数が2~10のアルキルメタクリレート(a1)単位の含有率が50質量%以上であると、得られるポリオレフィン系樹脂組成物のポリオレフィン系樹脂(B)中でのポリオレフィン系樹脂用加工助剤の分散性が良好となり溶融張力に優れる。 The alkyl methacrylate polymer (A) of the present invention is mainly composed of alkyl methacrylate (a1) units having 2 to 10 carbon atoms in the alkyl group.
In the alkyl methacrylate polymer (A), the content of alkyl methacrylate (a1) units having 2 to 10 carbon atoms in the alkyl group is 50% by mass or more in 100% by mass of all monomer units, and (a1) The unit content is preferably 70% by mass or more, and the (a1) unit content is more preferably 80% by mass or more.
When the content of the alkyl methacrylate (a1) unit having 2 to 10 carbon atoms in the alkyl group is 50% by mass or more, the polyolefin resin processing in the polyolefin resin (B) of the resulting polyolefin resin composition The dispersibility of the auxiliary agent becomes good and the melt tension is excellent.
アルキル基の炭素数が2~10のアルキルメタクリレート(a1)としては、例えば、エチルメタクリレート、n-プロピルメタクリレート、i-プロピルメタクリレート、n-ブチルメタクリレート、i-ブチルメタクリレート、sec-ブチルメタクリレート、t-ブチルメタクリレート、2-メチルブチルメタクリレート、3-メチルブチルメタクリレート、3-ペンチルメタクリレート、n-ヘキシルメタクリレート、シクロヘキシルメタクリレート、2-エチルヘキシルメタクリレート、n-オクチルメタクリレート、デシルメタクリレート、t-ブチルシクロヘキシルメタクリレートが挙げられる。これらは、1種を単独で用いてもよく2種以上を併用してもよい。 The alkyl methacrylate polymer (A) of the present invention can be obtained by polymerizing the monomer component (a) whose main component is an alkyl methacrylate (a1) having 2 to 10 carbon atoms in the alkyl group.
Examples of the alkyl methacrylate (a1) having 2 to 10 carbon atoms in the alkyl group include, for example, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, sec-butyl methacrylate, t- Examples thereof include butyl methacrylate, 2-methylbutyl methacrylate, 3-methylbutyl methacrylate, 3-pentyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, decyl methacrylate, and t-butylcyclohexyl methacrylate. These may be used alone or in combination of two or more.
他の単量体(a2)としては、例えば、メチルメタクリレート;ラウリルメタクリレート等のアルキル基の炭素数が10以上のアルキルメタクリレート;(メタ)アクリル酸;スチレン、α―メチルスチレン、クロルスチレン等の芳香族ビニル単量体;メチルアクリレート、エチルアクリレート、ブチルアクリレート等のアルキルアクリレート;(メタ)アクリロニトリル等のシアン化ビニル単量体;ビニルメチルエーテル、ビニルエチルエーテル等のビニルエーテル単量体;酢酸ビニル、酪酸ビニル等のカルボン酸ビニル単量体;エチレン、プロピレン、イソブチレン等のオレフィン系単量体;ブタジエン、イソプレン、ジメチルブタジエン等のジエン系単量体;4-(メタ)アクリロイルオキシ-2,2,6,6-テトラメチルピペリジン、4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン等の光安定化能基含有単量体が挙げられる。これらは、1種を単独で用いてもよく2種以上を併用してもよい。 As the monomer component (a), in addition to the alkyl methacrylate (a1) having 2 to 10 carbon atoms in the alkyl group, other monomer (a2) that can be copolymerized may be included as necessary.
Examples of the other monomer (a2) include methyl methacrylate; alkyl methacrylate having 10 or more carbon atoms in the alkyl group such as lauryl methacrylate; (meth) acrylic acid; aromatic such as styrene, α-methylstyrene, chlorostyrene, etc. Group vinyl monomers; alkyl acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate; vinyl cyanide monomers such as (meth) acrylonitrile; vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether; vinyl acetate and butyric acid Carboxylic acid vinyl monomers such as vinyl; Olefin monomers such as ethylene, propylene and isobutylene; Diene monomers such as butadiene, isoprene and dimethylbutadiene; 4- (meth) acryloyloxy-2,2,6 , 6-Tetramethylpiperidi 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine light stabilizing capability group-containing monomers, and the like. These may be used alone or in combination of two or more.
尚、本明細書において、「(メタ)アクリル」は、「アクリル」又は「メタクリル」を示す。 Among these, alkyl acrylate is preferable because it has good copolymerizability with alkyl methacrylate having 2 to 10 carbon atoms in the alkyl group and suppresses thermal decomposition of the alkyl methacrylate polymer (A).
In the present specification, “(meth) acryl” means “acryl” or “methacryl”.
アルキル基の炭素数が2~10のアルキルメタクリレート(a1)の含有率が50質量%以上であると、得られるポリオレフィン系樹脂組成物のポリオレフィン系樹脂(B)中でのポリオレフィン系樹脂用加工助剤の分散性が良好となり溶融張力に優れる。
他の単量体(a2)の含有率が50質量%以下であると、得られるポリオレフィン系樹脂組成物のポリオレフィン系樹脂(B)中でのポリオレフィン系樹脂用加工助剤の分散性が良好となり溶融張力に優れる。 The composition ratio of the monomer component (a) is such that the content of the alkyl methacrylate (a1) having 2 to 10 carbon atoms in the alkyl group is 50% by mass or more in 100% by mass of the monomer component (a). The content of the monomer (a2) is preferably 50% by mass or less, the content of (a1) is preferably 70% by mass or more, and the content of (a2) is preferably 30% by mass or less, (a1) It is more preferable that the content of is 80% by mass or more and the content of (a2) is 20% by mass or less.
When the content of the alkyl methacrylate (a1) having 2 to 10 carbon atoms in the alkyl group is 50% by mass or more, the processing aid for polyolefin resin in the polyolefin resin (B) of the resulting polyolefin resin composition is used. The dispersibility of the agent is improved and the melt tension is excellent.
When the content of the other monomer (a2) is 50% by mass or less, the dispersibility of the processing aid for polyolefin resin in the polyolefin resin (B) of the resulting polyolefin resin composition becomes good. Excellent melt tension.
これらの中でも、生産性が良好であることから、ラジカル重合が好ましい。 Examples of the polymerization method of the monomer component (a) include radical polymerization and ionic polymerization.
Among these, radical polymerization is preferable because of good productivity.
これらの中でも、アルキルメタクリレート系重合体(A)を粉体状又は顆粒状の形態で得られることから、乳化重合、懸濁重合が好ましい。 Examples of the polymerization form of the monomer component (a) include emulsion polymerization, soap-free polymerization, fine suspension polymerization, suspension polymerization, bulk polymerization, and solution polymerization.
Among these, emulsion polymerization and suspension polymerization are preferable because the alkyl methacrylate polymer (A) is obtained in a powdery or granular form.
これらの中でも、スルホン酸系塩化合物、硫酸系塩化合物、燐酸エステル系塩化合物等のアニオン性乳化剤が好ましい。 Examples of the emulsifier used when the monomer component (a) is polymerized by emulsion polymerization include an anionic emulsifier, a nonionic emulsifier, a polymer emulsifier, and a reactivity having an unsaturated double bond capable of radical polymerization in the molecule. Emulsifiers. These may be used alone or in combination of two or more.
Among these, anionic emulsifiers such as sulfonic acid salt compounds, sulfuric acid salt compounds, and phosphate ester salt compounds are preferable.
これらの中でも、極少量で分散安定性を保持できることから、アニオン系高分子化合物が好ましい。 Examples of the dispersion stabilizer used when the monomer component (a) is polymerized by suspension polymerization include poorly water-soluble inorganic compounds such as calcium phosphate, calcium carbonate, aluminum hydroxide, and starch silica; polyvinyl alcohol, polyethylene oxide, Nonionic polymer compounds such as cellulose derivatives; anionic polymer compounds such as poly (meth) acrylic acid and salts thereof, and copolymers of methacrylic acid esters and methacrylic acid and salts thereof. These may be used alone or in combination of two or more.
Among these, an anionic polymer compound is preferable because the dispersion stability can be maintained with a very small amount.
アルキルメタクリレート系重合体(A)を乳化重合で重合した場合において、重合体(A)のラテックスから重合体(A)を取り出す方法としては、例えば、凝析法、スプレードライ法、遠心分離法、凍結乾燥法が挙げられる。
これらの中でも、得られるアルキルメタクリレート系重合体(A)の粉体の均一性が良好となることから、凝析法、スプレードライ法であることが好ましい。 The alkyl methacrylate polymer (A) polymerized by various polymerization methods may be taken out of the polymerization system as powder or granules by a method suitable for each polymerization method.
In the case where the alkyl methacrylate polymer (A) is polymerized by emulsion polymerization, examples of the method for taking out the polymer (A) from the latex of the polymer (A) include a coagulation method, a spray drying method, a centrifugal separation method, A freeze-drying method is mentioned.
Of these, the coagulation method and the spray drying method are preferred because the uniformity of the resulting powder of the alkyl methacrylate polymer (A) becomes good.
凝析剤としては、例えば、塩酸、硫酸、硝酸、燐酸等の無機酸類;蟻酸、酢酸等の有機酸類;硫酸アルミニウム、硫酸マグネシウム、硫酸カルシウム等の無機塩類;酢酸カルシウム等の有機塩類が挙げられる。 As the coagulation method, for example, the alkyl methacrylate polymer (A) latex is brought into contact with a coagulant, and coagulated while stirring to form a slurry, followed by dehydration drying, whereby the alkyl methacrylate polymer (A) powder is obtained. The method of obtaining a body is mentioned.
Examples of the coagulant include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; organic acids such as formic acid and acetic acid; inorganic salts such as aluminum sulfate, magnesium sulfate, and calcium sulfate; and organic salts such as calcium acetate. .
スプレードライ法における出口温度としては、アルキルメタクリレート系重合体(A)の粉体の1次粒子への解砕性に優れることから、40~90℃であることが好ましく、40~80℃であることがより好ましい。 As the spray drying method, for example, the alkyl methacrylate polymer (A) latex is spray-dried with a spray dryer under the conditions of an inlet temperature of 120 ° C. to 220 ° C. and an outlet temperature of 40 to 90 ° C. A method for obtaining a powder of the combined body (A) is mentioned.
The outlet temperature in the spray drying method is preferably 40 to 90 ° C., and preferably 40 to 80 ° C., because the powder of the alkyl methacrylate polymer (A) has excellent crushability to primary particles. It is more preferable.
アルキルメタクリレート系重合体(A)の質量平均分子量が1万5000以上であると、得られるポリオレフィン系樹脂用加工助剤の溶融張力向上効果が優れる。また、アルキルメタクリレート系重合体(A)の質量平均分子量が14万5000以下であると、得られるポリオレフィン系樹脂組成物の流動性に優れる。
尚、本発明における質量平均分子量は、ゲルパーミエーションクロマトグラフィーを用いて測定される。 The mass average molecular weight of the alkyl methacrylate polymer (A) of the present invention is from 15,000 to 145,000, preferably from 20,000 to 130,000, and more preferably from 25,000 to 100,000. .
When the mass average molecular weight of the alkyl methacrylate polymer (A) is 15,000 or more, the effect of improving the melt tension of the resulting polyolefin resin processing aid is excellent. Moreover, it is excellent in the fluidity | liquidity of the polyolefin resin composition obtained as the mass average molecular weight of an alkyl methacrylate polymer (A) is 145,000 or less.
In addition, the mass average molecular weight in this invention is measured using a gel permeation chromatography.
連鎖移動剤としては、例えば、n-ドデシルメルカプタン、t-ドデシルメルカプタン、n-オクチルメルカプタン、n-テトラデシルメルカプタン、n-ヘキシルメルカプタン等のメルカプタン類;四塩化炭素、臭化エチレン等のハロゲン化物;α-メチルスチレンダイマーが挙げられる。これらは、1種を単独で用いてもよく2種以上を併用してもよい。
連鎖移動剤の使用量としては、アルキルメタクリレート系重合体(A)の質量平均分子量、用いる連鎖移動剤の種類、単量体成分(a)の構成比等に応じて、適宜調整することができる。 Examples of the method for adjusting the mass average molecular weight include a method for adjusting the amount of the polymerization initiator and a method for adjusting the amount of the chain transfer agent.
Examples of chain transfer agents include mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, n-tetradecyl mercaptan, n-hexyl mercaptan; halides such as carbon tetrachloride and ethylene bromide; α-methylstyrene dimer may be mentioned. These may be used alone or in combination of two or more.
The amount of chain transfer agent used can be appropriately adjusted according to the weight average molecular weight of the alkyl methacrylate polymer (A), the type of chain transfer agent used, the composition ratio of the monomer component (a), and the like. .
ポリオレフィン系樹脂用加工助剤は、アルキルメタクリレート系重合体(A)以外に、ポリオレフィン系樹脂(B)の本来の特性を損なわない範囲において、充填剤、難燃剤、安定化剤、滑剤、発泡剤等の各種添加剤を更に配合してもよい。 The processing aid for polyolefin resin of the present invention contains the alkyl methacrylate polymer (A) of the present invention.
The processing aids for polyolefin resins are fillers, flame retardants, stabilizers, lubricants, foaming agents as long as they do not impair the original properties of polyolefin resins (B) in addition to alkyl methacrylate polymers (A). Various additives such as these may be further blended.
オレフィン系単量体としては、例えば、エチレン、プロピレン、1-ブテン、1-ヘキセン、1-オクテン、1-デセンが挙げられる。
これらの中でも、得られる成形体の汎用性の観点から、エチレン、プロピレンが好ましい。 The polyolefin resin (B) used in the present invention is a homopolymer or copolymer of an olefin monomer, a copolymer of a dominant amount of an olefin monomer and a subordinate amount of a vinyl monomer, an olefin type The main component is a copolymer of a monomer and a diene monomer.
Examples of the olefin monomer include ethylene, propylene, 1-butene, 1-hexene, 1-octene and 1-decene.
Among these, ethylene and propylene are preferable from the viewpoint of versatility of the obtained molded body.
これらの中でも、得られる成形体の汎用性の観点から、ポリエチレン、ポリプロピレン、エチレン-プロピレン共重合体、エチレン-酢酸ビニル共重合体が好ましい。 Examples of the polyolefin resin (B) include low density polyethylene, ultra low density polyethylene, ultra low density polyethylene, linear low density polyethylene, high density polyethylene, ultra high molecular weight polyethylene, polypropylene, ethylene-propylene copolymer, polybutene. And ethylene-vinyl acetate copolymer. These may be used alone or in combination of two or more.
Among these, polyethylene, polypropylene, an ethylene-propylene copolymer, and an ethylene-vinyl acetate copolymer are preferable from the viewpoint of versatility of the obtained molded body.
ポリプロピレンとしては、例えば、「ノバテックPP FY4」、「ノバテックPP MA3」、「ノバテックPP BC03B」、「ノバテックPP BC06C」、「ウィンテック」、「ニューコン」、「ニューフォーマー」(商品名、日本ポリプロ(株)製);「プライムポリプロ J105G」、「プライムポリプロ B241」(商品名、(株)プライムポリマー製)が挙げられる。 Examples of polyethylene include “Novatech HD HJ360”, “Novatech HD HY420”, “Novatech HD HE421”, “Novatech HD JF313” (trade name, manufactured by Nippon Polyethylene Co., Ltd.); “Hi-X” (trade name, Co., Ltd.) ) Prime polymer); “Mineron”, “Mineace”, “Minefan” (trade name, Sankyo Polyethylene Co., Ltd.).
Examples of polypropylene include “Novatech PP FY4”, “Novatech PP MA3”, “Novatech PP BC03B”, “Novatech PP BC06C”, “Wintech”, “Newcon”, “Newformer” (trade name, Japan) Polypro Co., Ltd.); “Prime Polypro J105G”, “Prime Polypro B241” (trade name, manufactured by Prime Polymer Co., Ltd.).
これらの中でも、得られる成形体の汎用性の観点から、オレフィン系エラストマー、スチレン系エラストマーが好ましい。 Examples of the thermoplastic elastomer (C) used in the present invention include thermoplastic elastomers such as olefin elastomers, styrene elastomers, polyester elastomers, polyamide elastomers, polyurethane elastomers; natural rubber, polyisobutylene, polyisoprene, chloroprene. Natural or synthetic rubbers such as rubber, butyl rubber, nitrile butyl rubber and the like can be mentioned. These may be used alone or in combination of two or more.
Among these, an olefin elastomer and a styrene elastomer are preferable from the viewpoint of versatility of the obtained molded body.
ポリオレフィン系樹脂(B)と熱可塑性エラストマー(C)の含有率としては、得られる成形品の用途に応じて適宜設定することができる。 The polyolefin resin composition of the present invention contains a polyolefin resin processing aid and a polyolefin resin (B), and further contains a thermoplastic elastomer (C) as necessary.
The contents of the polyolefin resin (B) and the thermoplastic elastomer (C) can be appropriately set according to the use of the obtained molded product.
このような樹脂としては、例えば、「ミラストマー5030N」、「ミラストマー6030N」、「ミラストマー7030N」、「ミラストマー8030N」、「ミラストマー2600B」(商品名、三井化学(株)製);「サーモラン5800B」、「サーモラン5850N」、「サーモラン3855B」(商品名、三菱化学(株)製);「エスポレックス3785」、「エスポレックス820」、「エスポレックス822」(商品名、住友化学(株)製);「サントプレーン 101-55」、「サントプレーン121-68W228」、「サントプレーン121-50M100」(商品名、エクソンモービル社製)が挙げられる。これらは、1種を単独で用いてもよく2種以上を併用してもよい。 As the resin used for the polyolefin resin composition, a resin in which the polyolefin resin (B) and the thermoplastic elastomer (C) are already blended may be used.
Examples of such resins include “Miralastomer 5030N”, “Miralastomer 6030N”, “Miralastomer 7030N”, “Miralastomer 8030N”, “Miralastomer 2600B” (trade name, manufactured by Mitsui Chemicals, Inc.); "Thermo Run 5850N", "Thermo Run 3855B" (trade name, manufactured by Mitsubishi Chemical Corporation); "Esporex 3785", "Esporex 820", "Esporex 822" (trade name, manufactured by Sumitomo Chemical Co., Ltd.); “Santplane 101-55”, “Santplane 121-68W228”, “Santplane 121-50M100” (trade name, manufactured by ExxonMobil Co., Ltd.). These may be used alone or in combination of two or more.
ポリオレフィン系樹脂用加工助剤の前記配合量が0.1質量部以上であると、得られるポリオレフィン系樹脂組成物の溶融張力と流動性に優れる。また、ポリオレフィン系樹脂用加工助剤の前記配合量が20質量部以下であると、ポリオレフィン系樹脂(B)の本来の特性を損なわない。
尚、本明細書において、ポリオレフィン系樹脂(B)と熱可塑性エラストマー(C)の合計100質量部とは、熱可塑性エラストマー(C)が0質量部である場合を含む。 The blending amount of the processing aid for polyolefin resin of the present invention is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass in total of the polyolefin resin (B) and the thermoplastic elastomer (C). More preferably, it is 0.5 to 10 parts by mass.
When the blending amount of the processing aid for polyolefin resin is 0.1 parts by mass or more, the melt tension and fluidity of the resulting polyolefin resin composition are excellent. Moreover, the original characteristic of polyolefin resin (B) is not impaired as the said compounding quantity of the processing aid for polyolefin resin is 20 mass parts or less.
In the present specification, the total of 100 parts by mass of the polyolefin resin (B) and the thermoplastic elastomer (C) includes the case where the thermoplastic elastomer (C) is 0 part by mass.
充填剤としては、例えば、炭酸カルシウム、炭酸マグネシウム、硫酸カルシウム、硫酸バリウム、水酸化マグネシウム、水酸化アルミニウム、タルク、マイカ、カオリン、チタンホワイト、ホワイトカーボン、カーボンブラック、ガラス繊維、炭素繊維が挙げられる。これらは、1種を単独で用いてもよく2種以上を併用してもよい。
充填剤の配合量としては、ポリオレフィン系樹脂(B)と熱可塑性エラストマー(C)の合計100質量部に対して、0.1~400質量部であることが好ましい。
充填剤の前記配合量が0.1質量部以上であると、充填剤の配合効果が充分に発現する。また、充填剤の前記配合量が400質量部以下であると、ポリオレフィン系樹脂(B)の本来の特性を損なわない。 The polyolefin resin composition may further contain various additives such as a filler, a flame retardant, a stabilizer, a lubricant, a foaming agent, a plasticizer, and a rubber softener as necessary.
Examples of the filler include calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, magnesium hydroxide, aluminum hydroxide, talc, mica, kaolin, titanium white, white carbon, carbon black, glass fiber, and carbon fiber. . These may be used alone or in combination of two or more.
The blending amount of the filler is preferably 0.1 to 400 parts by mass with respect to 100 parts by mass in total of the polyolefin resin (B) and the thermoplastic elastomer (C).
When the blending amount of the filler is 0.1 parts by mass or more, the blending effect of the filler is sufficiently exhibited. Moreover, the original characteristic of polyolefin resin (B) is not impaired as the said compounding quantity of a filler is 400 mass parts or less.
難燃剤の配合量としては、難燃剤の種類にもよるが、ポリオレフィン系樹脂(B)と熱可塑性エラストマー(C)の合計100質量部に対して、10~200質量部であることが好ましい。 Examples of the flame retardant include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, diisopropylphenyl phosphate, tris (chloroethyl) ) Phosphate ester compounds such as phosphate, alkoxy-substituted bisphenol A bisphosphate, hydroquinone bisphosphate, resorcin bisphosphate, trioxybenzene triphosphate; tetrabromobisphenol A, decabromodiphenyl oxide, hexabromocyclododecane, octabromodiphenyl ether, bistribromo Phenoxyethane, ethylene Strebrobromophthalimide, tribromophenol, halogenated epoxy oligomer obtained by reaction of halogenated bisphenol A and epihalohydrin, carbonate oligomer containing halogenated bisphenol A, halogenated polystyrene, chlorinated polyolefin, polychlorinated And halogen-containing compounds such as vinyl; metal oxides; and sulfamic acid compounds. These may be used alone or in combination of two or more.
The blending amount of the flame retardant is preferably 10 to 200 parts by mass with respect to a total of 100 parts by mass of the polyolefin resin (B) and the thermoplastic elastomer (C), although it depends on the type of flame retardant.
無機発泡剤としては、例えば、二酸化炭素、空気、窒素等が挙げられる。
揮発性発泡剤としては、例えば、プロパン、n-ブタン、i-ブタン、ペンタン等の脂肪族炭化水素;シクロブタン、シクロペンタン等の環式脂肪族炭化水素;トリクロロフロロメタン、ジクロロジフロロメタン、ジクロロテトラフロロエタン、メチルクロリド、エチルクロリド、メチレンクロリド等のハロゲン化炭化水素が挙げられる。
分解型発泡剤としては、例えば、アゾジカルボンアミド、ジニトロソペンタメチレンテトラミン、アゾビスイソブチロニトリル、重炭酸ナトリウムが挙げられる。
これらの発泡剤は、1種を単独で用いてもよく2種以上を併用してもよい。
発泡剤の配合量としては、発泡剤の種類にもよるが、ポリオレフィン系樹脂(B)と熱可塑性エラストマー(C)の合計100質量部に対して、0.1~25質量部であることが好ましい。 Examples of the foaming agent include inorganic foaming agents, volatile foaming agents, and decomposable foaming agents.
Examples of the inorganic foaming agent include carbon dioxide, air, and nitrogen.
Examples of the volatile blowing agent include aliphatic hydrocarbons such as propane, n-butane, i-butane and pentane; cycloaliphatic hydrocarbons such as cyclobutane and cyclopentane; trichlorofluoromethane, dichlorodifluoromethane and dichloromethane. Halogenated hydrocarbons such as tetrafluoroethane, methyl chloride, ethyl chloride, methylene chloride and the like can be mentioned.
Examples of the decomposable foaming agent include azodicarbonamide, dinitrosopentamethylenetetramine, azobisisobutyronitrile, and sodium bicarbonate.
These foaming agents may be used individually by 1 type, and may use 2 or more types together.
The blending amount of the foaming agent is 0.1 to 25 parts by mass with respect to a total of 100 parts by mass of the polyolefin resin (B) and the thermoplastic elastomer (C), although it depends on the type of the foaming agent. preferable.
ゴム用軟化剤としては、例えば、日本油脂(株)製のNAソルベント(イソパラフィン系炭化水素油、商品名)、出光興産(株)のPW-90(n-パラフィン系プロセスオイル、商品名)、出光石油化学(株)製のIP-ソルベント2835(合成イソパラフィン系炭化水素、99.8質量%以上のイソパラフィン、商品名)、三光化学工業(株)製のネオチオゾール(n-パラフィン系プロセスオイル、商品名)が挙げられる。これらは、1種を単独で用いてもよく2種以上を併用してもよい。
ゴム用軟化剤の配合量としては、ポリオレフィン系樹脂(B)と熱可塑性エラストマー(C)の合計100質量部に対して、10~300質量部であることが好ましく、より好ましくは50~200質量部である。
ゴム用軟化剤の前記配合量が10質量部以上であると、柔軟性付与効果が充分に発現する。また、ゴム用軟化剤の前記配合量が300質量部以下であると、ポリオレフィン系樹脂(B)の本来の特性を損なわない。 The rubber softener is generally a mixture of an aromatic ring, a naphthene ring, and a paraffin chain. Among the softeners for rubber, process oils called paraffin and process oils called naphthenic are used among mineral oil rubber softeners. Besides these, white oil, mineral oil Ethylene and α-olefin oligomers, low molecular weight polybutadiene, low molecular weight polybutadiene, paraffin wax, and liquid paraffin can be used. Of these, paraffinic process oil is preferably used.
Examples of rubber softeners include NA Solvent (isoparaffinic hydrocarbon oil, trade name) manufactured by NOF Corporation, PW-90 (n-paraffinic process oil, trade name) of Idemitsu Kosan Co., Ltd., IP-solvent 2835 (synthetic isoparaffinic hydrocarbon, 99.8% by mass or more isoparaffin, trade name) manufactured by Idemitsu Petrochemical Co., Ltd., neothiozole (n-paraffinic process oil, product manufactured by Sanko Chemical Co., Ltd.) Name). These may be used alone or in combination of two or more.
The blending amount of the rubber softening agent is preferably 10 to 300 parts by mass, more preferably 50 to 200 parts by mass with respect to 100 parts by mass in total of the polyolefin resin (B) and the thermoplastic elastomer (C). Part.
When the blending amount of the rubber softener is 10 parts by mass or more, the flexibility imparting effect is sufficiently exhibited. Moreover, the original characteristic of polyolefin resin (B) is not impaired as the said compounding quantity of the softener for rubbers is 300 mass parts or less.
また、本発明のポリオレフィン系樹脂用加工助剤を配合することで、ポリオレフィン系樹脂(B)との相容性が低い各種添加剤のブリードアウトを抑制する効果も期待できる。 Various additives such as fillers, flame retardants, stabilizers, lubricants, foaming agents, plasticizers, rubber softeners, etc. are not sufficiently blended when not sufficiently dispersed in the polyolefin resin (B). It may become. By blending the processing aid for polyolefin resin of the present invention, not only the molding processability of the resulting polyolefin resin composition is improved, but also the dispersibility of various additives in the polyolefin resin (B) is improved. In order to improve, further blending effects can be expected.
Moreover, the effect which suppresses the bleed-out of various additives with low compatibility with polyolefin resin (B) can be anticipated by mix | blending the processing aid for polyolefin resin of this invention.
溶融混練方法としては、本発明のポリオレフィン系樹脂用加工助剤、ポリオレフィン系樹脂(B)、必要に応じて、熱可塑性エラストマー(C)、各種添加剤を一括で溶融混練してもよく、ポリオレフィン系樹脂用加工助剤、熱可塑性エラストマー(C)の一部を混合してマスターバッチを作製した後、残部のポリオレフィン系樹脂(B)、必要に応じて、熱可塑性エラストマー(C)の一部、各種添加剤を配合する多段階で混合してもよい。 The polyolefin resin composition of the present invention comprises a polyolefin resin processing aid, a polyolefin resin (B), and if necessary, a thermoplastic elastomer (C) and various additives, followed by extrusion kneading and roll kneading. It adjusts by melt-kneading by well-known methods, such as.
As the melt kneading method, the polyolefin resin processing aid of the present invention, the polyolefin resin (B), and if necessary, the thermoplastic elastomer (C) and various additives may be melt kneaded in a lump. After preparing a master batch by mixing a part of the processing aid for thermoplastic resin and the thermoplastic elastomer (C), the remainder of the polyolefin resin (B), if necessary, part of the thermoplastic elastomer (C) The various additives may be mixed in multiple stages.
成形方法としては、例えば、押出成形、射出成形、カレンダー成形、ブロー成形、熱成形、発泡成形、溶融紡糸が挙げられる。 The molded article of the present invention can be obtained by molding the polyolefin resin composition of the present invention.
Examples of the molding method include extrusion molding, injection molding, calendar molding, blow molding, thermoforming, foam molding, and melt spinning.
尚、実施例中の「部」及び「%」は、それぞれ「質量部」及び「質量%」を示す。
実施例、比較例における各物性の測定は、以下の(1)~(6)の方法による。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
In the examples, “parts” and “%” indicate “parts by mass” and “% by mass”, respectively.
The physical properties in Examples and Comparative Examples are measured by the following methods (1) to (6).
得られたアルキルメタクリレート系重合体(A)の質量平均分子量及び数平均分子量を、アルキルメタクリレート系重合体(A)のテトラヒドロフラン可溶分を試料として、ゲルパーミエーションクロマトグラフィー(機種名「HLC-8220」、東ソー(株)製)、カラム(商品名「TSK-GEL SUPER MULTIPORE HZ-H」、東ソー(株)製、内径4.6mm×長さ15cm×2本)を用い、溶離液テトラヒドロフラン、測定温度40℃の条件で測定を行ない、標準ポリスチレンによる検量線から求めた。
更に、下記の式より分子量分布を算出した。
分子量分布=(質量平均分子量)/(数平均分子量) (1) Mass average molecular weight and molecular weight distribution The mass average molecular weight and number average molecular weight of the resulting alkyl methacrylate polymer (A) are gel permeation using the tetrahydrofuran solubles of the alkyl methacrylate polymer (A) as a sample. Chromatography (model name “HLC-8220”, manufactured by Tosoh Corporation), column (trade name “TSK-GEL SUPER MULTIPORE HZ-H”, manufactured by Tosoh Corporation, inner diameter 4.6 mm × length 15 cm × 2 pieces) ) Was used under the conditions of eluent tetrahydrofuran and measurement temperature of 40 ° C., and obtained from a calibration curve using standard polystyrene.
Furthermore, molecular weight distribution was computed from the following formula.
Molecular weight distribution = (mass average molecular weight) / (number average molecular weight)
ポリオレフィン系樹脂用加工助剤を、8メッシュの篩に通し、以下の基準により粉体としての取扱性を評価した。
○:篩通過量が80%以上
△:篩通過量が10%以上~80%未満
×:篩通過量が10%未満 (2) Powder handling property The processing aid for polyolefin resin was passed through an 8-mesh sieve, and the handling property as a powder was evaluated according to the following criteria.
○: Sieve passage amount is 80% or more △: Sieve passage amount is 10% or more to less than 80% ×: Sieve passage amount is less than 10%
得られたポリオレフィン系樹脂組成物を、キャピラリー式レオメーター(機種名「ツインキャピラリーレオメーター RH-7型」、ROSAND社製)を用いて、ダイス径=φ1mm、L/D=16、温度190℃の条件で、一定量(1.57cm3/分)で押出し、ストランドを一定速度(3m/分)で引き取り、溶融張力を測定した。
尚、溶融張力は、押出成形性、ブロー成形性、発泡成形性等の成形加工性を判断する指標の一つであり、溶融張力の向上は、成形加工性の向上と見なし得る。 (3) Melt tension Using the capillary type rheometer (model name “Twin Capillary Rheometer RH-7”, manufactured by ROSAND), the resulting polyolefin resin composition was subjected to die diameter = φ1 mm, L / D = 16. Extruded at a constant amount (1.57 cm 3 / min) under the condition of a temperature of 190 ° C., the strand was drawn at a constant speed (3 m / min), and the melt tension was measured.
The melt tension is one of the indicators for determining the moldability such as extrusion moldability, blow moldability, and foam moldability, and the improvement of the melt tension can be regarded as the improvement of the moldability.
得られたポリオレフィン系樹脂組成物を、メルトインデクサー(機種名「L-243-1531」、(株)テクノ・セブン製)を用いて、荷重2.16kg、測定温度230℃の条件で、ASTM D1238に準拠して、MFRを測定した。 (4) MFR (melt flow rate)
The obtained polyolefin resin composition was subjected to ASTM using a melt indexer (model name “L-243-1531”, manufactured by Techno Seven Co., Ltd.) under the conditions of a load of 2.16 kg and a measurement temperature of 230 ° C. MFR was measured according to D1238.
得られた異型押出成形品のエッジを目視により観察し、以下の基準により成形加工性を評価した。
○:図1の[1]~[4]でエッジ切れがない。
×:図1の[1]~[3]でエッジ切れがなく、[4]でエッジ切れがある。 (5) Molding processability The edge of the obtained profile extrusion-molded product was visually observed, and the molding processability was evaluated according to the following criteria.
○: No edge break in [1] to [4] in FIG.
×: No edge break in [1] to [3] in FIG. 1, and edge break in [4].
ポリオレフィン系樹脂組成物の溶融張力が低く、且つ滑性が低い場合、押出機のダイス周辺に目ヤニが発生し、異型押出成形品に目ヤニが付着する場合がある。
得られた異型押出成形品20cm中の[3]のエッジに付着した目ヤニの個数を計測し、以下の基準により目ヤニ評価を行なった。
○:目ヤニなし
△:目ヤニの数が1個~5個
×:目ヤニの数が6個以上 (6) Evaluation of Eye Dispersion When the melt tension of the polyolefin-based resin composition is low and the slipperiness is low, an eye discoloration may occur around the die of the extruder, and the discoloration may adhere to the profile extrusion molded product.
The number of spears adhering to the edge of [3] in the obtained profile extrusion molded product 20 cm was measured, and the spear evaluation was performed according to the following criteria.
○: No eye crease △: Number of
温度計、窒素導入管、冷却管及び攪拌装置を備えたセパラブルフラスコ(容量5リットル)に、脱イオン水300部(3,000グラム)、i-ブチルメタクリレート98部、n-ブチルアクリレート2部、n-オクチルメルカプタン0.22部、ドデシルベンゼンスルホン酸ナトリウム1.1部を投入し、このセパラブルフラスコに窒素気流を通じることにより、フラスコ内雰囲気の窒素置換を行なった。次いで、内温を60℃まで昇温させ、過硫酸カリウム0.15部、脱イオン水5部を加えた。その後、加熱攪拌を2時間継続して重合を終了し、アルキルメタクリレート系重合体(A1)のラテックスを得た。
得られたアルキルメタクリレート系重合体(A1)のラテックスを、酢酸カルシウム5部を含む70℃の温水400部中に滴下した後、90℃まで昇温して凝析させた。得られた凝析物を分離洗浄後、60℃で16時間乾燥させて、アルキルメタクリレート系重合体(A1)を得た。重合体(A1)の質量平均分子量は11万であり、分子量分布は1.9であった。
得られたアルキルメタクリレート系重合体(A1)を、ポリオレフィン系樹脂用加工助剤(1)とした。加工助剤(1)の粉体取扱性を評価した結果を、表1に示す。 [Example 1]
In a separable flask (
The resulting latex of alkyl methacrylate polymer (A1) was dropped into 400 parts of 70 ° C. hot water containing 5 parts of calcium acetate, and then heated to 90 ° C. for coagulation. The obtained coagulated product was separated and washed, and then dried at 60 ° C. for 16 hours to obtain an alkyl methacrylate polymer (A1). The mass average molecular weight of the polymer (A1) was 110,000, and the molecular weight distribution was 1.9.
The obtained alkyl methacrylate polymer (A1) was used as a polyolefin resin processing aid (1). The results of evaluating the powder handling property of the processing aid (1) are shown in Table 1.
単量体成分の組成、連鎖移動剤量を表1に記載のように変更したこと以外は、実施例1と同様にして、アルキルメタクリレート系重合体(A2)~(A13)を得た。
得られたアルキルメタクリレート系重合体(A2)~(A13)を、ポリオレフィン系樹脂用加工助剤(2)~(13)とした。 [Examples 2 to 7, Comparative Examples 1 to 6]
Alkyl methacrylate polymers (A2) to (A13) were obtained in the same manner as in Example 1 except that the composition of the monomer components and the amount of chain transfer agent were changed as shown in Table 1.
The resulting alkyl methacrylate polymers (A2) to (A13) were used as polyolefin resin processing aids (2) to (13).
脱イオン水300部、ラウリルメタクリレート98部、n-ブチルアクリレート2部、n-オクチルメルカプタン0.7部、ドデシルベンゼンスルホン酸ナトリウム1.1部、t-ブチルハイドロパーオキサイド0.1部を、ホモミキサーを用いて10,000rpmで2分間攪拌した後、ホモジナイザーを用いて圧力200kg/cm2で強制乳化し、乳化混合物を得た。
この乳化混合物を温度計、窒素導入管、冷却管及び攪拌装置を備えたセパラブルフラスコに仕込み、窒素雰囲気下で内温を60℃まで昇温させ、硫酸第一鉄0.0001部、エチレンジアミン四酢酸二ナトリウム塩0.0003部、ロンガリット0.3部、脱イオン水5部を投入した。その後、加熱攪拌を2時間継続して重合を終了し、アルキルメタクリレート系重合体(A14)のラテックスを得た。
得られたアルキルメタクリレート系重合体(A14)のラテックスを、酢酸カルシウム5部を含む25℃の冷水400部中に滴下して凝析させた。得られた凝析物を分離洗浄後、50℃で16時間乾燥させて、アルキルメタクリレート系重合体(A14)を得た。
得られたアルキルメタクリレート系重合体(A14)を、ポリオレフィン系樹脂用加工助剤(14)とした。 [Comparative Example 7]
300 parts of deionized water, 98 parts of lauryl methacrylate, 2 parts of n-butyl acrylate, 0.7 part of n-octyl mercaptan, 1.1 parts of sodium dodecylbenzenesulfonate, 0.1 part of t-butyl hydroperoxide After stirring for 2 minutes at 10,000 rpm using a mixer, forced emulsification was performed using a homogenizer at a pressure of 200 kg / cm 2 to obtain an emulsified mixture.
This emulsified mixture was charged into a separable flask equipped with a thermometer, a nitrogen introduction tube, a cooling tube and a stirrer, and the internal temperature was raised to 60 ° C. under a nitrogen atmosphere. 0.0001 part of ferrous sulfate, ethylenediamine 0.0003 part of acetic acid disodium salt, 0.3 part of Rongalite and 5 parts of deionized water were added. Thereafter, heating and stirring were continued for 2 hours to complete the polymerization, and an alkyl methacrylate polymer (A14) latex was obtained.
The resulting latex of alkyl methacrylate polymer (A14) was dripped into 400 parts of 25 ° C. cold water containing 5 parts of calcium acetate for coagulation. The obtained coagulated product was separated and washed, and then dried at 50 ° C. for 16 hours to obtain an alkyl methacrylate polymer (A14).
The obtained alkyl methacrylate polymer (A14) was used as a polyolefin resin processing aid (14).
単量体成分の組成、連鎖移動剤量を表1に記載のように変更したこと以外は、比較例7と同様にして、アルキルアクリレート系重合体(A15)を得た。
得られたアルキルアクリレート系重合体(A15)を、ポリオレフィン系樹脂用加工助剤(15)とした。 [Comparative Example 8]
An alkyl acrylate polymer (A15) was obtained in the same manner as in Comparative Example 7 except that the composition of the monomer component and the amount of the chain transfer agent were changed as shown in Table 1.
The obtained alkyl acrylate polymer (A15) was used as a polyolefin resin processing aid (15).
脱イオン水300部、ラウリルメタクリレート70部、n-オクチルメルカプタン0.49部、ドデシルベンゼンスルホン酸ナトリウム1.1部、t-ブチルハイドロパーオキサイド0.07部を、ホモミキサーを用いて10,000rpmで2分間攪拌した後、ホモジナイザーを用いて圧力200kg/cm2で強制乳化し、乳化混合物を得た。
この乳化混合物を温度計、窒素導入管、冷却管及び攪拌装置を備えたセパラブルフラスコに仕込み、窒素雰囲気下で内温を60℃まで昇温させ、硫酸第一鉄0.0001部、エチレンジアミン四酢酸二ナトリウム塩0.0003部、ロンガリット0.21部、脱イオン水5部を投入した。その後、加熱攪拌を2時間継続して重合を終了し、1段目の重合を終了した。
その後、内温を60℃に保持した後、ロンガリット0.09部、脱イオン水5部を投入し、メチルメタクリレート30部、n-オクチルメルカプタン0.21部、t-ブチルハイドロパーオキサイド0.03部の混合物を30分間かけて滴下した。その後、加熱攪拌を2時間継続して重合を終了し、アルキルメタクリレート系重合体(A16)のラテックスを得た。
得られたアルキルメタクリレート系重合体(A16)のラテックスを、酢酸カルシウム5部を含む70℃の温水400部中に滴下した後、90℃まで昇温して凝析させた。得られた凝析物を分離洗浄後、60℃で16時間乾燥させてアルキルメタクリレート系重合体(A16)を得た。
得られたアルキルメタクリレート系重合体(A16)を、ポリオレフィン系樹脂用加工助剤(16)とした。 [Comparative Example 9]
300 parts of deionized water, 70 parts of lauryl methacrylate, 0.49 parts of n-octyl mercaptan, 1.1 parts of sodium dodecylbenzenesulfonate, 0.07 part of t-butyl hydroperoxide were added at 10,000 rpm using a homomixer. The mixture was forcibly emulsified with a homogenizer at a pressure of 200 kg / cm 2 to obtain an emulsified mixture.
This emulsified mixture was charged into a separable flask equipped with a thermometer, a nitrogen introduction tube, a cooling tube and a stirrer, and the internal temperature was raised to 60 ° C. under a nitrogen atmosphere. 0.0001 part of ferrous sulfate, ethylenediamine 0.0003 part of acetic acid disodium salt, 0.21 part of Rongalite and 5 parts of deionized water were added. Then, heating and stirring were continued for 2 hours to complete the polymerization, and the first stage polymerization was completed.
Thereafter, after maintaining the internal temperature at 60 ° C., 0.09 part of Rongalite and 5 parts of deionized water were added, 30 parts of methyl methacrylate, 0.21 part of n-octyl mercaptan, 0.03 part of t-butyl hydroperoxide. Part of the mixture was added dropwise over 30 minutes. Thereafter, heating and stirring were continued for 2 hours to complete the polymerization, and an alkyl methacrylate polymer (A16) latex was obtained.
The resulting latex of the alkyl methacrylate polymer (A16) was dropped into 400 parts of 70 ° C. hot water containing 5 parts of calcium acetate, and then heated to 90 ° C. for coagulation. The obtained coagulated product was separated and washed, and then dried at 60 ° C. for 16 hours to obtain an alkyl methacrylate polymer (A16).
The obtained alkyl methacrylate polymer (A16) was used as a polyolefin resin processing aid (16).
i-BMA:i-ブチルメタクリレート
MMA :メチルメタクリレート
EMA :エチルメタクリレート
n-BMA:n-ブチルメタクリレート
LMA :ラウリルメタクリレート
n-BA :n-ブチルアクリレート
i-BA :i-ブチルアクリレート
tBH :t-ブチルハイドロパーオキサイド
nOM :n-オクチルメルカプタン The abbreviations in Table 1 are as shown below.
i-BMA: i-butyl methacrylate MMA: methyl methacrylate EMA: ethyl methacrylate n-BMA: n-butyl methacrylate LMA: lauryl methacrylate n-BA: n-butyl acrylate i-BA: i-butyl acrylate tBH: t-butyl hydro Peroxide nOM: n-octyl mercaptan
ポリオレフィン系樹脂(B)としてポリプロピレン系樹脂(商品名「ノバテックPP FY4」、日本ポリプロ(株)製)100部(2,000グラム)、及びポリオレフィン系樹脂用加工助剤(1)~(13)、(16)を表2に記載のように配合し、ハンドブレンドで混合した。尚、加工助剤(8)は塊状であったため、粉砕したものを用いた。
その後、φ30mm同方向二軸押出機(機種名「BT-30」、(株)プラスチック工学研究所製、L/D=30)を用いて、スクリュー回転数200rpm、シリンダー温度200℃の条件で溶融混練し、ポリオレフィン系樹脂組成物を得た。
得られたポリオレフィン系樹脂組成物の溶融張力及びMFRを、表2に示す。 [Examples 8 to 17, Comparative Examples 10 to 17]
Polypropylene resin (trade name “NOVATEC PP FY4”, manufactured by Nippon Polypro Co., Ltd.) 100 parts (2,000 grams) as polyolefin resin (B), and processing aids for polyolefin resin (1) to (13) (16) was blended as described in Table 2 and mixed by hand blending. Since the processing aid (8) was in a lump shape, it was pulverized.
Thereafter, using a φ30 mm same-direction twin screw extruder (model name “BT-30”, manufactured by Plastic Engineering Laboratory Co., Ltd., L / D = 30), melted under the conditions of a screw rotation speed of 200 rpm and a cylinder temperature of 200 ° C. By kneading, a polyolefin resin composition was obtained.
Table 2 shows the melt tension and MFR of the obtained polyolefin-based resin composition.
ポリオレフィン系樹脂(B)としてポリプロピレン系樹脂(商品名「ノバテックPP FY4」、日本ポリプロ(株)製)、熱可塑性エラストマー(C)として水添スチレン系エラストマー(商品名「タフテック H1062」、旭化成ケミカルズ(株)製)、及びポリオレフィン系樹脂用加工助剤(1)~(3)、(7)~(10)、(12)、(13)を表3に記載のように配合し、ハンドブレンドで混合した。尚、加工助剤(8)は塊状であったため、粉砕したものを用いた。
その後、φ30mm同方向二軸押出機(機種名「BT-30」、(株)プラスチック工学研究所製、L/D=30)を用いて、スクリュー回転数200rpm、シリンダー温度200℃の条件で溶融混練し、ポリオレフィン系樹脂組成物を得た。
得られたポリオレフィン系樹脂組成物の溶融張力及びMFRを、表3に示す。 [Examples 18 to 21, Comparative Examples 18 to 23]
Polypropylene resin (trade name “Novatech PP FY4”, manufactured by Nippon Polypro Co., Ltd.) as polyolefin resin (B), hydrogenated styrene elastomer (trade name “Tuftec H1062”, Asahi Kasei Chemicals Corporation) as thermoplastic elastomer (C) ), And processing aids for polyolefin resins (1) to (3), (7) to (10), (12), (13) as shown in Table 3, Mixed. Since the processing aid (8) was in a lump shape, it was pulverized.
Thereafter, using a φ30 mm same-direction twin screw extruder (model name “BT-30”, manufactured by Plastic Engineering Laboratory Co., Ltd., L / D = 30), melted under the conditions of a screw rotation speed of 200 rpm and a cylinder temperature of 200 ° C. By kneading, a polyolefin resin composition was obtained.
Table 3 shows the melt tension and MFR of the obtained polyolefin-based resin composition.
ポリオレフィン系樹脂(B)と熱可塑性エラストマー(C)を含む樹脂として「サントプレーン121-68W228」(商品名、エクソンモービル社製)、及びポリオレフィン系樹脂用加工助剤(1)、(2)、(9)、(10)、(16)を表4に記載のように配合し、実施例8と同様にして溶融混練し、ポリオレフィン系樹脂組成物を得た。
得られたポリオレフィン系樹脂組成物を異型ダイス(図1)を取り付けたφ30mm単軸押出機(機種名「GM-30」、(株)ジー・エム・エンジニアリング製、L/D=35)を用いて、スクリュー回転数30rpm、バレル温度190℃の条件で溶融混練し、異型押出成形品を得た。
尚、異型ダイスから押出した成形品は、押出方向と平行に一定速度で引き取り、20cm引き取ったところで切断した。
得られた異型押出成形品の成形加工性及び目ヤニ評価結果を表4に示す。 [Examples 22 and 23, Comparative Examples 24-27]
As a resin containing a polyolefin resin (B) and a thermoplastic elastomer (C), “Santoprene 121-68W228” (trade name, manufactured by ExxonMobil), and a processing aid for polyolefin resin (1), (2), (9), (10) and (16) were blended as shown in Table 4, and melt-kneaded in the same manner as in Example 8 to obtain a polyolefin resin composition.
Using the obtained polyolefin resin composition, a φ30 mm single screw extruder (model name “GM-30”, manufactured by GM Engineering Co., Ltd., L / D = 35) equipped with a modified die (FIG. 1). The mixture was melt-kneaded under the conditions of a screw rotation speed of 30 rpm and a barrel temperature of 190 ° C. to obtain a profile extrusion molded product.
Incidentally, the molded product extruded from the odd-shaped die was taken at a constant speed parallel to the extrusion direction, and cut when it was taken 20 cm.
Table 4 shows the moldability of the obtained profile extrusion-molded product and the evaluation results of the eyes.
質量平均分子量が本発明の範囲を下回るポリオレフィン系樹脂用加工助剤(8)は、塊状となり、粉体としての取扱性が悪かった(比較例1)。
単量体単位の種類が本発明の範囲外となるポリオレフィン系樹脂用加工助剤(14)及び(15)は、高粘度の糊状物であるため、粉体としての取扱性が悪かった(比較例7、8)。ハンドブレンドやフィーダーによる供給が困難であり、加工助剤としての使用が困難であった。 As is apparent from Table 1, the processing aids (1) to (7) for polyolefin resins of Examples 1 to 7 have good handling properties as powders. The processing aids (1) to (7) are easily mixed with the polyolefin resin when hand blended and can be stably supplied with a feeder or the like, so that they can be uniformly kneaded with the polyolefin resin.
The polyolefin resin processing aid (8) having a mass average molecular weight lower than the range of the present invention was agglomerated and poor in handling as a powder (Comparative Example 1).
The polyolefin resin processing aids (14) and (15) whose monomer units are out of the scope of the present invention are high-viscosity paste-like materials, and thus the handling properties as powders were poor ( Comparative Examples 7 and 8). Supply with a hand blend or a feeder is difficult, and use as a processing aid is difficult.
ポリオレフィン系加工助剤を含まないポリオレフィン系樹脂組成物は、溶融張力及びMFRのバランスが充分でなく、成形加工性に劣った(比較例17、23)。
質量平均分子量が本発明の範囲を下回るポリオレフィン系樹脂用加工助剤(8)を含有するポリオレフィン系樹脂組成物は、溶融張力が向上しなかった(比較例10、18)。 As is apparent from Tables 2 and 3, the polyolefin resin compositions containing the processing aids (1) to (7) for polyolefin resins of the present invention were excellent in melt tension and MFR (Examples 8 to 21). ).
A polyolefin resin composition not containing a polyolefin processing aid did not have a sufficient balance between melt tension and MFR and was inferior in molding processability (Comparative Examples 17 and 23).
The polyolefin resin composition containing the polyolefin resin processing aid (8) having a mass average molecular weight below the range of the present invention did not improve the melt tension (Comparative Examples 10 and 18).
アルキルメタクリレート単位のアルキル基の炭素数が本発明の範囲外となるポリオレフィン系樹脂用加工助剤(13)は、ポリオレフィン系樹脂中での分散性が不充分であった(比較例15、22)。比較例15では、ポリオレフィン系樹脂(B)との相容性が低くストランドを引き取ることができなかったため、溶融張力は測定できなかった。比較例22では、溶融張力が低かった。 Polyolefin resin compositions containing polyolefin resin processing aids (9) to (12) having a mass average molecular weight exceeding the range of the present invention have an inadequate balance between melt tension and MFR and are inferior in molding processability. (Comparative Examples 11 to 14, 19 to 21).
The processing aid for polyolefin resin (13) in which the carbon number of the alkyl group of the alkyl methacrylate unit is outside the range of the present invention has insufficient dispersibility in the polyolefin resin (Comparative Examples 15 and 22). . In Comparative Example 15, since the compatibility with the polyolefin resin (B) was low and the strand could not be taken up, the melt tension could not be measured. In Comparative Example 22, the melt tension was low.
質量平均分子量が本発明の範囲を上回るポリオレフィン系樹脂用加工助剤(9)、(10)を含有するポリオレフィン系樹脂組成物及び、単量体単位の種類が本発明の範囲外であり、二段で重合したポリオレフィン系樹脂用加工助剤(16)を含有するポリオレフィン系樹脂組成物は、成形加工性、目ヤニの抑制効果に劣った(比較例24~26)。 As is clear from Table 4, the polyolefin resin composition to which the processing aid for polyolefin resin according to the present invention was added was excellent in the effect of suppressing eye strain as well as improved moldability (Examples 22 and 23). .
The polyolefin resin composition containing the processing aids for polyolefin resins (9) and (10) having a mass average molecular weight exceeding the range of the present invention, and the types of monomer units are outside the scope of the present invention. The polyolefin resin composition containing the processing aid (16) for polyolefin resin polymerized in stages was inferior in molding processability and the effect of suppressing eye strain (Comparative Examples 24-26).
図2から明らかなように、ポリオレフィン系樹脂用加工助剤の質量平均分子量と、ポリオレフィン系加工助剤を含有するポリオレフィン系樹脂組成物の流動性との関係において、相関があることがわかる。しかしながら、同様に質量平均分子量と溶融張力の関係を示した図3から明らかなように、本発明の質量平均分子量の範囲では、特異的に溶融張力が優れていることがわかる。 From Table 2, FIG. 2 shows the relationship between the weight average molecular weights of Examples 8 to 10 and Comparative Examples 10 to 12 and MFR. (The processing aids for polyolefin resins of Examples 8 to 10 and Comparative Examples 10 to 12 are composed of the same monomer component and have different mass average molecular weights.)
As is clear from FIG. 2, it can be seen that there is a correlation between the mass average molecular weight of the polyolefin resin processing aid and the fluidity of the polyolefin resin composition containing the polyolefin processing aid. However, as apparent from FIG. 3 showing the relationship between the mass average molecular weight and the melt tension, it can be seen that the melt tension is particularly excellent in the range of the mass average molecular weight of the present invention.
Claims (8)
- アルキル基の炭素数が2~10のアルキルメタクリレート(a1)単位を主成分として含有し、質量平均分子量が1万5000~14万5000であるアルキルメタクリレート系重合体(A)を含む、ポリオレフィン系樹脂用加工助剤。 Polyolefin resin containing an alkyl methacrylate polymer (A) containing an alkyl methacrylate (a1) unit having 2 to 10 carbon atoms in the alkyl group as a main component and having a mass average molecular weight of 15,000 to 145,000. Processing aids.
- 前記(a1)単位が、アルキル基の炭素数が4のアルキルメタクリレート単位である、請求項1記載のポリオレフィン系樹脂用加工助剤。 The processing aid for polyolefin resin according to claim 1, wherein the unit (a1) is an alkyl methacrylate unit having an alkyl group having 4 carbon atoms.
- 前記(a1)単位が、i-ブチルメタクリレート単位である、請求項1記載のポリオレフィン系樹脂用加工助剤。 The processing aid for polyolefin resin according to claim 1, wherein the unit (a1) is an i-butyl methacrylate unit.
- アルキルメタクリレート系重合体(A)の質量平均分子量が2万~10万である、請求項1記載のポリオレフィン系樹脂用加工助剤。 The processing aid for polyolefin resin according to claim 1, wherein the alkyl methacrylate polymer (A) has a mass average molecular weight of 20,000 to 100,000.
- 請求項1~4のいずれか1項に記載のポリオレフィン系樹脂用加工助剤及びポリオレフィン系樹脂(B)を含むポリオレフィン系樹脂組成物。 A polyolefin resin composition comprising the polyolefin resin processing aid according to any one of claims 1 to 4 and a polyolefin resin (B).
- 請求項1~4のいずれか1項に記載のポリオレフィン系樹脂用加工助剤、ポリオレフィン系樹脂(B)及び熱可塑性エラストマー(C)を含むポリオレフィン系樹脂組成物。 A polyolefin resin composition comprising the polyolefin resin processing aid according to any one of claims 1 to 4, a polyolefin resin (B), and a thermoplastic elastomer (C).
- 請求項5記載のポリオレフィン系樹脂組成物を成形して得られる成形品。 A molded product obtained by molding the polyolefin resin composition according to claim 5.
- 請求項6記載のポリオレフィン系樹脂組成物を成形して得られる成形品。 A molded product obtained by molding the polyolefin resin composition according to claim 6.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020127013416A KR101419618B1 (en) | 2009-11-26 | 2010-11-24 | Processing aid for polyolefin resins, polyolefin resin compositions, and molded products |
JP2010549982A JP6150266B2 (en) | 2009-11-26 | 2010-11-24 | Processing aid for polyolefin resin, polyolefin resin composition and molded product |
EP10833228.9A EP2505605B1 (en) | 2009-11-26 | 2010-11-24 | Processing aid for polyolefin resins, polyolefin resin compositions, and molded products |
CN201080053674.8A CN102648241B (en) | 2009-11-26 | 2010-11-24 | Processing aid for polyolefin resins, polyolefin resin compositions, and molded products |
US13/512,258 US20120277379A1 (en) | 2009-11-26 | 2010-11-24 | Processing aid for polyolefin-based resin, polyolefin-based resin composition and molded article |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009268539 | 2009-11-26 | ||
JP2009-268539 | 2009-11-26 | ||
JP2010-233387 | 2010-10-18 | ||
JP2010233387 | 2010-10-18 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011065382A1 true WO2011065382A1 (en) | 2011-06-03 |
Family
ID=44066487
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2010/070936 WO2011065382A1 (en) | 2009-11-26 | 2010-11-24 | Processing aid for polyolefin resins, polyolefin resin compositions, and molded products |
Country Status (7)
Country | Link |
---|---|
US (1) | US20120277379A1 (en) |
EP (1) | EP2505605B1 (en) |
JP (2) | JP6150266B2 (en) |
KR (1) | KR101419618B1 (en) |
CN (1) | CN102648241B (en) |
TW (1) | TWI612063B (en) |
WO (1) | WO2011065382A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140037972A1 (en) * | 2011-04-14 | 2014-02-06 | Wencai Xu | Modifier composition for polyolefin, polyolefin for packaging and flexible packaging film |
JP2016020415A (en) * | 2014-07-14 | 2016-02-04 | 三菱レイヨン株式会社 | Processing aid for acrylic elastomer resin, acrylic elastomer resin composition and molded body |
JP2018532002A (en) * | 2015-08-31 | 2018-11-01 | ローム アンド ハース カンパニーRohm And Haas Company | Processing aid for foam molding, vinyl chloride resin-based foam molding composition containing the same, and foam molding product |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2565230B1 (en) * | 2010-04-27 | 2015-09-09 | Mitsubishi Rayon Co., Ltd. | Dispersant for additive for polyolefin resin, polyolefin resin composition, and molded article |
WO2021240694A1 (en) * | 2020-05-27 | 2021-12-02 | 東洋スチレン株式会社 | Resin composition |
CN114174418A (en) * | 2019-08-27 | 2022-03-11 | 东洋苯乙烯股份有限公司 | Resin composition |
CN110655726A (en) * | 2019-10-09 | 2020-01-07 | 佛山市丰正科技有限公司 | Antioxidant for rubber, preparation method and application thereof |
CN112679669B (en) * | 2020-12-25 | 2023-03-24 | 广州熵能创新材料股份有限公司 | External lubricant for PVC resin processing and preparation method thereof |
CN114369197B (en) * | 2022-01-18 | 2022-10-11 | 熵能创新材料(珠海)有限公司 | Polyalkylacrylate processing aid and melt-processable composition containing same |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01247409A (en) * | 1988-03-29 | 1989-10-03 | Mitsubishi Rayon Co Ltd | Processing aid for thermoplastic resin and thermoplastic resin composition containing the same |
JPH0657151A (en) * | 1986-10-16 | 1994-03-01 | Mitsubishi Rayon Co Ltd | Thermoplastic resin composition |
JPH11100479A (en) | 1997-07-30 | 1999-04-13 | Mitsubishi Rayon Co Ltd | Thermoplastic resin composition and masterbatch containing the composition |
JP2000319516A (en) * | 1999-03-08 | 2000-11-21 | Mitsubishi Rayon Co Ltd | Auxiliary for processing resin and thermoplastic resin composition using the same |
JP2001031826A (en) * | 1999-05-19 | 2001-02-06 | Mitsubishi Rayon Co Ltd | Processing aid, vinyl, chloride-based resin composition using the same and production of molded article using the same composition |
JP2003020376A (en) * | 2001-07-10 | 2003-01-24 | Kanegafuchi Chem Ind Co Ltd | Processability improver and vinyl chloride resin composition containing it |
WO2006112192A1 (en) * | 2005-03-30 | 2006-10-26 | Kaneka Corporation | (meth)acrylic polymer and vinyl chloride resin composition containing the same |
JP2008037955A (en) * | 2006-08-03 | 2008-02-21 | Mitsubishi Rayon Co Ltd | Thermoplastic resin composition and molded product thereof |
JP2009060936A (en) | 2007-09-04 | 2009-03-26 | Konica Minolta Medical & Graphic Inc | Biological signal analysis apparatus and program for biological signal analysis apparatus |
WO2009060936A1 (en) * | 2007-11-07 | 2009-05-14 | Mitsubishi Rayon Co., Ltd. | Powdery processing aid for polyolefin-based resins, method of producing the same, resin composition and molded article |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
PH25743A (en) * | 1987-10-14 | 1991-10-18 | Rhom | Adhesive compositions containing low molecular weight polymer additives |
US4912169A (en) * | 1987-10-14 | 1990-03-27 | Rohm And Haas Company | Adhesive compositions containing low molecular weight polymer additives |
US5571581A (en) * | 1991-06-14 | 1996-11-05 | Toyoda Gosei Co., Ltd. | Long sandwich molded article |
JPH0693049A (en) * | 1992-09-09 | 1994-04-05 | Mitsubishi Petrochem Co Ltd | Methacrylic random copolymer and its production |
WO1996019513A1 (en) * | 1994-12-22 | 1996-06-27 | Mitsubishi Rayon Co., Ltd. | Block copolymer and process for producing the same |
US6344493B2 (en) * | 1997-08-22 | 2002-02-05 | Mitsubishi Rayon Co., Ltd. | Melt tension improver for polyolefin resins and process for producing the same |
JPH11106438A (en) * | 1997-10-08 | 1999-04-20 | Mitsubishi Rayon Co Ltd | Flowability modifier for thermoplastic resin and thermoplastic resin composition containing the same |
JP4120075B2 (en) * | 1998-12-02 | 2008-07-16 | 東ソー株式会社 | Highly foamable polyolefin resin composition and use thereof |
CN101432369A (en) * | 2006-04-26 | 2009-05-13 | 株式会社钟化 | Thermoplastic resin composition and process for production thereof |
WO2008062860A1 (en) * | 2006-11-24 | 2008-05-29 | Mitsubishi Rayon Co., Ltd. | Stabilizer for polyolefin resin and stabilized polyolefin resin composition |
TWI568784B (en) * | 2009-04-10 | 2017-02-01 | 三菱麗陽股份有限公司 | Additive for thermoplastic resin, production method thereof, thermoplastic resin composition and shaped article |
-
2010
- 2010-11-24 KR KR1020127013416A patent/KR101419618B1/en active IP Right Grant
- 2010-11-24 JP JP2010549982A patent/JP6150266B2/en active Active
- 2010-11-24 WO PCT/JP2010/070936 patent/WO2011065382A1/en active Application Filing
- 2010-11-24 US US13/512,258 patent/US20120277379A1/en not_active Abandoned
- 2010-11-24 CN CN201080053674.8A patent/CN102648241B/en active Active
- 2010-11-24 EP EP10833228.9A patent/EP2505605B1/en active Active
- 2010-11-25 TW TW099140806A patent/TWI612063B/en active
-
2015
- 2015-06-02 JP JP2015112392A patent/JP2015155555A/en not_active Withdrawn
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0657151A (en) * | 1986-10-16 | 1994-03-01 | Mitsubishi Rayon Co Ltd | Thermoplastic resin composition |
JPH01247409A (en) * | 1988-03-29 | 1989-10-03 | Mitsubishi Rayon Co Ltd | Processing aid for thermoplastic resin and thermoplastic resin composition containing the same |
JPH11100479A (en) | 1997-07-30 | 1999-04-13 | Mitsubishi Rayon Co Ltd | Thermoplastic resin composition and masterbatch containing the composition |
JP2000319516A (en) * | 1999-03-08 | 2000-11-21 | Mitsubishi Rayon Co Ltd | Auxiliary for processing resin and thermoplastic resin composition using the same |
JP2001031826A (en) * | 1999-05-19 | 2001-02-06 | Mitsubishi Rayon Co Ltd | Processing aid, vinyl, chloride-based resin composition using the same and production of molded article using the same composition |
JP2003020376A (en) * | 2001-07-10 | 2003-01-24 | Kanegafuchi Chem Ind Co Ltd | Processability improver and vinyl chloride resin composition containing it |
WO2006112192A1 (en) * | 2005-03-30 | 2006-10-26 | Kaneka Corporation | (meth)acrylic polymer and vinyl chloride resin composition containing the same |
JP2008037955A (en) * | 2006-08-03 | 2008-02-21 | Mitsubishi Rayon Co Ltd | Thermoplastic resin composition and molded product thereof |
JP2009060936A (en) | 2007-09-04 | 2009-03-26 | Konica Minolta Medical & Graphic Inc | Biological signal analysis apparatus and program for biological signal analysis apparatus |
WO2009060936A1 (en) * | 2007-11-07 | 2009-05-14 | Mitsubishi Rayon Co., Ltd. | Powdery processing aid for polyolefin-based resins, method of producing the same, resin composition and molded article |
Non-Patent Citations (1)
Title |
---|
See also references of EP2505605A4 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140037972A1 (en) * | 2011-04-14 | 2014-02-06 | Wencai Xu | Modifier composition for polyolefin, polyolefin for packaging and flexible packaging film |
US9518179B2 (en) * | 2011-04-14 | 2016-12-13 | Beijing Institute Of Graphic Communication | Modifier composition for polyolefin, polyolefin for packaging and flexible packaging film |
JP2016020415A (en) * | 2014-07-14 | 2016-02-04 | 三菱レイヨン株式会社 | Processing aid for acrylic elastomer resin, acrylic elastomer resin composition and molded body |
JP2018532002A (en) * | 2015-08-31 | 2018-11-01 | ローム アンド ハース カンパニーRohm And Haas Company | Processing aid for foam molding, vinyl chloride resin-based foam molding composition containing the same, and foam molding product |
Also Published As
Publication number | Publication date |
---|---|
CN102648241B (en) | 2014-12-03 |
TWI612063B (en) | 2018-01-21 |
EP2505605A4 (en) | 2013-11-06 |
KR20120093307A (en) | 2012-08-22 |
JP6150266B2 (en) | 2017-06-21 |
JP2015155555A (en) | 2015-08-27 |
EP2505605A1 (en) | 2012-10-03 |
TW201120062A (en) | 2011-06-16 |
US20120277379A1 (en) | 2012-11-01 |
CN102648241A (en) | 2012-08-22 |
EP2505605B1 (en) | 2015-06-10 |
KR101419618B1 (en) | 2014-07-14 |
JPWO2011065382A1 (en) | 2013-04-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6150266B2 (en) | Processing aid for polyolefin resin, polyolefin resin composition and molded product | |
KR101544232B1 (en) | Powdery processing aid for polyolefin-based resins, method of producing the same, resin composition and molded article | |
KR101484829B1 (en) | Dispersant for additive for polyolefin resin, polyolefin resin composition, and molded article | |
TWI568784B (en) | Additive for thermoplastic resin, production method thereof, thermoplastic resin composition and shaped article | |
JP5673991B2 (en) | Dispersibility improver, thermoplastic resin composition, and molded article | |
JP5221439B2 (en) | Polyolefin resin composition for foam molding, process for producing the same, and foam molded article | |
JP5237185B2 (en) | Thermoplastic resin composition and molded body | |
JP2015227420A (en) | Polyolefin resin composition and molding | |
JP2003277571A (en) | Olefinic thermoplastic elastomer and its molded product | |
JP2014224207A (en) | Matte effect regulator, matting agent composition, and thermoplastic resin composition containing matte effect regulator and molded article thereof | |
JP2005112924A (en) | Thermoplastic resin composition | |
JP2010120981A (en) | Polyolefin-based resin composition for calendering and method for obtaining formed product thereof | |
JP2010053295A (en) | Processing aid for styrene elastomer, styrene elastomer composition and molded article | |
JP2012046579A (en) | Compatibilizer for polar resin and polyolefin resin, thermoplastic resin composition, and molded body | |
JP2011246688A (en) | Dispersibility improver for flame retardant, thermoplastic resin composition and molded article |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080053674.8 Country of ref document: CN |
|
ENP | Entry into the national phase |
Ref document number: 2010549982 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10833228 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20127013416 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010833228 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13512258 Country of ref document: US Ref document number: 4656/DELNP/2012 Country of ref document: IN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1201002455 Country of ref document: TH |
|
NENP | Non-entry into the national phase |
Ref country code: DE |